DE2549370A1 - METHOD AND DEVICE FOR GENERATING HYDROGEN FROM WATER - Google Patents

Description

Title: Process and device for the production of hydrogen from water

description

The invention relates to a method for producing hydrogen by displacement from water with subsequent regeneration of a reactant. The invention also relates to an apparatus to carry out this procedure. The invention is thus concerned with the production of hydrogen and in particular with a process and a device for the reactive generation of hydrogen from water.

The 1970s have become a critical period for humanity. Energy consumption is consecutive all over the world the population explosion, accelerated industrialization, economic growth and social development continued gone up. One has to start from a continuation of the fierce demand for all forms of energy everywhere in the world. The continuing drive for increased industrialization, Mechanization and better living standards will continue

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Desire for all types of fuel, propellant or fuel, in particular in developing countries. This growth will further complicate already existing complex problems related to the development of fuel supplies and their adequate delivery, conversion and use exist. The public is becoming increasingly aware that the social and environmental problems with the manufacture and the Consumption of fuel. In view of this, there has become an intricate limitation on the extraction, Processing and use of energy sources result. Efficiency in generating energy is one of the most critical important technical problems of the day. The better kinds of ours natural fuels, namely the best and most easily accessible supplies of coal, petroleum and natural gas unquestionably towards their exhaustion and it is crucial Meaning that every possible effort is made to use these supplies in a sensible manner. It is totally wrong, the coals, the oath oil and the natural gas of the earth as fuel, which is converted into thermal energy. When these priceless supplies are converted into heat, they are forever lost. However, when transformed into one of the thousands of chemical products we desperately need are, then the supplies are preserved and are useful in a far more valuable form.

Thus, there is a need for more efficient energy conversion processes and devices and a different fuel supply for the entire earth needs to be developed, regardless of cost that the natural remedies are not in the way.

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wasted as it is done today. There is considerable agreement among technicians that hydrogen is the offers the most practical solution to the omnipresent problem described. Environmental considerations also leave incineration of hydrogen as a fuel appear to be cheap, since the products resulting from the combustion are completely pure are. The invention now seeks a method and an apparatus for producing hydrogen in tremendous economic quantities and create at economically interesting costs.

The law of conservation of energy and the first law of thermodynamics will now be discussed. It is well known that there are many types of energy, e.g. heat, radiation (light) and work energy and mechanical, electrical and magnetic energy. Due to the law of conservation of energy, the physical and chemical processes discussed below are correct agree that energy is neither created nor destroyed can be. When a certain amount of a certain type of energy disappears, a corresponding amount reappears of a different kind of energy. Thermal energy is often considered in a separate class from all other types of energy because, Experiments show that heat cannot always be completely converted from one form to another as well as it can into heat. This does not contradict the law of the conservation of energy, because this law only requires that if there is actually heat is converted into another form of energy, a corresponding amount of energy of the other form appears. Because the invention is concerned with these fundamental scientific laws,

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these are mentioned in detail when they are relevant. If it makes sense or is meaningful for the following description is not only the thermodynamic one to be taken into account Law in detail, but also equations are given, which are related to the respective explanations stand.

When reference is made here to a thermodynamic system, it is implied that it is any substance under consideration includes. E.g. 1 mole of a certain gas can be used under certain Consider volume, pressure and temperature relationships as a system. A certain amount of water is also required for a ber a certain temperature and a certain pressure just as much a system as a certain amount of solid iron together with a certain one Amount of oxygen at 25 ° C and 1 atm. The environment consists of everything that is outside the respective system is located. In particular, the environmental setting is something that is subject to change is touched in the system. A closed system does not exchange matter with its surroundings, but it can do energy exchange in some forms, e.g. in the form of heat. An isolated one The system does not exchange matter or energy with its environment.

When it says here that a system is in a given state This means that the system is fully described and all relevant conditions are specified in detail are. For example, if the system is an ideal gas, then its state is defined by any three of the following four properties

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ien given: temperature T, pressure P, volume V and number of moles N .. Three of these properties are sufficient because the fourth property is derived from the law PV - nRT that applies to ideal gases or from the Van der Waals equation (P ) (V - b) = RT for

yields a single mole of gas. In a system that is composed of a certain number of moles of a pure liquid or pure pesticide, temperature and pressure are sufficient to describe the state of a stable system, that is, a system in a state of equilibrium. If, for example, one considers 1 mole of liquid water at 20 ° C and under a total pressure of 1 atm, then tables of physical constants can be seen that the density is 1.0 g / cm, and it can be seen that 1 mole (18, 0 g) of liquid H ₃ O occupies a volume of 18.0 cm. In the case of pesticides, various crystalline modifications can be present without restriction, even if only one form is stable. the crystalline modification must also be specified in detail in this pail. Finally, if the system is a mixture of two or more substances in equilibrium, the amount of each substance present must also be reported.

The state of a thermodynamic system is in the present one Description identifiable if specified in detail;

1) All substances that make up the system,

2) the amount and the physical state, namely gaseous, liquid or solid and, if necessary, the crystalline modification, any of these substances, as well as,

3) the temperature and pressure of the system.

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2 5 4 9 3 7 Γ)

Transformation of a system refers to any process by which a System from a specified initial state to a specified one Final state passes. Every chemical reaction is a transformation of a system; includes the initial state of the system the reactants and the final state includes the products.

Enthalpy is the term used to describe the heat that is exchanged during conversions under constant pressure. This term appears in the First Law of Thermodynamics and describes the heat exchanged between the system and the environment. A conversion at constant pressure P, in which no work other than the unavoidable pressure-volume work is carried out _f is w - - P «. \ V. For such a conversion, the First Law, λ E = q + w, can be given as: AE - q - P J ^ V, where P = constant.

Since P is always a positive quantity, the term PäV has a negative sign when work is being done on the system by the environment (the system contracts if .Δ V - Vp-V., Where the index letters f and i denote End or final and the initial or initial state denote ^ is negative) and a positive sign if work is carried out by the system on the environment (the system expands if &. V-Vp-V _{1 is} positive is), and the exchanged heat q is simply the heat of conversion at constant pressure; this is then called the enthalpy change of the transformation J ^ H. Hence, the First Law can be applied to any constant pressure conversion as far as

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only pressure-volume work is required, specify as: ZiE -ZsH - PAV

and ^ H = AE + PAV.

Thermochemistry is the term used to describe the quantitative study of enthalpy (heat) changes that accompany chemical reactions. The quantitative enthalpy relations with which thermochemistry is concerned are based on the law of conservation of energy and are valid for any given change to be considered here, regardless of the structural interpretation given here of the chemical change itself. Thermochemical facts have been continually used to determine what the more significant factors of the observed energy factors are and to test the validity of the conclusions drawn here.

During a reaction, the temperature or the pressure of the system may rise or fall, but these changes affect the Values of ^ i H do not indicate the change in enthalpy of the reaction is when the final state of the system, i.e. the products, the temperature and the pressure of the initial state of the system come back on took. It is then to be established that the enthalpy of a system is a thermodynamic function (a function of the State), so that the enthalpy accompanying a reaction * ^ H = Hx. - H. independent of each intermediate state or of intermediate states is. If it's not relevant to the equation, then the physical state, temperature and pressure, will each the reactants and the products of a thermochemical reaction

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tion is called the default state. Any change in enthalpy which includes substances in their standard states is therefore referred to as the standard change in enthalpy at the specific temperature and is represented by SH. .

The enthalpy of atomization (A ^H _a Tomi ^ ^{is the Ener} S ^ie> the conversion of 1 mole of a substance in its gaseous atoms at the same temperature and pressure is to be assigned. It is always energy required to any substance, solid, liquid or gaseous substances, into its gaseous atoms so that the enthalpy of the atomization ^ i H _a ^ omiz is always positive, that is, absorbed by the thermal system.

The term enthalpy of dissociation (Δη ^) denotes the energy required to transform a gaseous covalent molecule into its individual gaseous atoms while remaining the same Temperature and constant pressure is to be assigned. For the elements that at 25 ° C and 1 atm as gaseous diatomic molecules exist, the enthalpy of dissociation is as great as the enthalpy of given in published tables Atomization.

Enthalpy of ionization (AHj _j Js It is well known that it is necessary To supply energy to an electron from a gaseous one Atom to separate and to form a monopositive gaseous ion, and must be supplied with a correspondingly larger amount of energy in order to additionally separate one or more electrons from the monopositive gaseous ion. Therefore the

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Enthalpy change / ft of separation of an electron from a neutral one Atom or a positive ion always has a positive value. The ΔΗ of the ionization of a gaseous atom to a gasför ^ This positive ion is called the ionization energy. Vice versa is the change in enthalpy that can be assigned to a process, by which a gaseous atom picks up an electron to form a gaseous mononegative ion, simply electron affinity of the element. Usually the values of the ionization energies and the electron affinities of elements for Processes at 25 ° C and 1 atm are given, although in practical circumstances such reactions do not proceed under these conditions.

The terms enthalpy of melting (JH-), evaporation (Λ H) and sublimation (A ^H _SU hi) denote the energy required to convert 1 mole of a pesticide into a liquid, a liquid into a vapor and of a solid are to be assigned in a vaporous state. Again, both the reactant and the conversion product are at the same temperature and pressure. Energy is always required to convert a solid into its liquid or vapor state and a liquid substance into its vapor state at a constant temperature. Hence & _fug > ^ subi ^and ^ vap are ^always positive. If a certain amount of heat energy is required to melt 1 mole of a solid or to vaporize 1 mole of a liquid, then the same amount of heat is released as the melt solidifies or the vapor liquefies. Hence J-

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the heat of solidification of a substance is equal to its heat of fusion, but with the negative sign, and correspondingly the heat of liquefaction of a gas is opposite and equal to that Heat of vaporization.

The standard enthalpy of formation (., \ H ■) of a compound is defined as the heat attributable to the reaction that generates 1 mole of the compound from its elements, with each element initially in its standard state and at the same temperature as the formed connection is located. All elements in the standard state are usually assigned an enthalpy of formation that is equal to zero. The standard enthalpy of formation ^ H _f of compounds are usually given at 25 ° C. This regulation has been adopted here. Usually the Λ h2 of a compound does not have the ability to split the compound into its elements, or the compound is stable against splitting into its elements. On the other hand, if ^ Ή ° £ _{Ο has} a sufficiently large positive value, the compound tends to split spontaneously into its elements at room temperature.

The enthalpy changes with temperature. The enthalpy H of a system under constant pressure always increases with temperature, as the following considerations show. For every system that experiences a transformation at constant pressure and with the sole occurrence of pressure-volume work, the relationship applies: Λ E - / N ₁ H - ΡΛΗ. The internal energy of a system is directly proportional to its temperature, so there is a rise in temperature

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positive ΛE means. Since most systems expand when the temperature rises, P ^ \ V is positive and we can conclude that an increase in temperature means an increase in the enthalpy of the system, where ΔΗ is positive, ie that H _{f is} greater than H ₁ .

The molar heat capacity C of a substance at constant temperature is the specific amount of heat required to raise the temperature of 1 mole of any substance by 1 degree. Therefore, in a system consisting of a pure substance, the value of ö H is related to the heat capacity C by the following expression; ^ H = C x / \ T, where £ r = T _f -T ₁ * This expression assumes that C has a constant value within the considered temperature range T. - T _f. In fact, the heat capacity C at constant temperature for solid and liquid substances is independent of temperature, provided that the temperature range is not very large; in the case of gases, however, it changes considerably. The C value of many substances is precisely known.

With all substances, the increase in enthalpy that occurs when the temperature rises takes place in accordance with a law that _{applies to H 2} O, although of course the values of the corresponding enthalpies of different substances can be considerably different at the same temperature, especially because the melting and boiling points are different for different substances can differ by 1000 degrees or more.

Since every property of a system, its change during a

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Reaction depends only on the initial and final state, if a thermodynamic puncture is, a new puncture, namely the entropy of the system, can be defined. Entropy is denoted by the symbol S * ^: and the change in entropy for a reaction at constant temperature T is:

Λ s - -A ^ -

Since T is always positive, Λ S is positive (i.e. the entropy increases of the system) j when the system absorbs heat from the environment (q - positive) and the entropy S of the system decreases (i.e. is / 3s negative) if the system gives off heat to the environment (q = negative). According to the previous definition, the entropy S of a system in units of energy is divided by degrees more absolute Expressed temperature. Since thermodynamic calculations usually use the mole as the basic amount of a substance, As Expressed in units of cal / mol χ degrees K. This unit will

, q is called the entropy unit (eu). The equation Λ S - ^ r

means in words: For every conversion at constant temperature, the entropy change Λ S is equal to the heat that is _{exchanged by the system with the environment under reversible conditions q rev} , divided by the absolute temperature T at which the heat exchange takes place. Polically, if the value of rq remains the same, the value of Λ S is the opposite of the absolute temperature T

Γβν '

reverses proportionally.

Summary: Entropy is a thermodynamic puncture that is a measure of a disturbance in a system that is twofold. Namely, the disturbance is a positional disturbance, which is a disturbance of molecular arrangement, and an energy disorder, which is a disruption of energy distribution in terms of possible

Ver

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divisions of energies among all molecules of the system. ';. As the temperature gets lower, the entropy decreases each System, since both the position disturbance and the energy disturbance are absent; actually is at the lowest possible temperature, at absolute zero, the entropy of any substance present in the form of a perfect crystal to be taken as zero.

Free energy of a system: If the work done by a system is ^w _use f _u i _max negative, the transformation can occur spontaneously; if the work done on a system is W - -, positive, the conversion does not occur spontaneously and work must be used to complete the conversion.

^W usefulmax = A ^H "<W ^and ^ rev - ^T ^ ^{3 and W} usefulmax

^W usefulmax in turn ^represents the change performance of the system at useful work, the system at a constant Temperetur and constant pressure from a specific initial state to a final state specific transitions. This ability of the system to do useful work when it is in a given state is called the Glbbs free energy, indicated by G. Therefore: W _usefulmax ■ = G _f - G _± = ΛG and

-tAs

These equations say that when a system transitions from a specific initial state to a specific final state at constant temperature and pressure, the change in the free energy of the system, Λ G = 6 _f - G ₁ * equals the maximum usable work which is to be assigned to the conversion.

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Therefore, if ^w _use f _u r _max is positive (the system work done), the free energy of the system increases in the conversion (Λ G is positive). If conversely W _ef . -, is negative (work done by the system), the free energy of the system decreases (AG is negative). If temperature and pressure are constant, the change in free energy AG is equal to the change in enthalpy £ H minus the product of absolute temperature T and the change in entropy Λ S. If we consider the units included in the equation .Ag ^ Ah - T As, and if we express A H in cal / mol, T in degrees K and ΛS in cal / moi χ degrees, then jtS G is to be expressed in cal / mol. Δ G thus represents the amount of energy per mole that is free to do useful work when a system changes from a specific initial to a specific final state.

The ^ iG values of some special processes are often identified by putting the abbreviated name of the process as an index behind the symbol Λ G, as was done previously with the Al values. For example, ^ G _{becomes fus} , Δ G _y and Aß _d . _lss written to indicate that it is the change in free energy of fusion, vaporization, and dissociation of a molecular substance into its isolated atoms.

The expression standard free energy of formation (AG ^. _M ) of a compound is used to indicate the change in free energy in such a reaction in which a specific compound, at a certain temperature and pressure, out of its, at the same temperature in its Standard state

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union elements is formed. By definition, all elements have an AG _f equal to zero in their standard state.

The temperature has an influence on the A G of a reaction. The value depends on the change in free energy Λ G for a specific reaction, i.e. the ability of the reaction to occur spontaneously to a large extent on the temperature at which the reaction takes place. In other words: a reaction that a certain temperature and a certain pressure is thermodynamically impossible (G ^ positive), can at a higher temperature thermodynamically possible (AG = negative). Indeed the change from a thermodynamically impossible to a thermodynamically possible reaction is primarily the result of Effect of the absolute temperature T on the size of the T As energy expression.

The following applies to every reaction in which the entropy of a system increases (disturbance reaction): If the reaction cannot take place spontaneously at a given temperature because of a large unfavorable J \, H (strongly endothermic reaction), then a rise in temperature does the favorable TAS factor is relatively more significant.

Consequently, there is always a certain temperature, even if it is sometimes extremely high, at which the favorable TAs expression finally the unfavorable A Η-expression outweighs, so that the eaktion is thermodynamically permissible. A kind of endothermic reaction that, provided the temperature is high enough, always works can occur spontaneously, the dissociation of substances (EIe-

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elements and compounds) into their atoms. In the process of atomizing a substance, the products always have a greater entropy than the reactants and the process leads to an increase in entropy (i \ S is positive). Of course, a large amount of energy is usually required for an atomization reaction, that is, Λ H _{atoniiz has a} large positive value, because atomization involves the breaking of the strong chemical bonds which the atoms of the reactant in the molecule or in the ionic crystal or in the metallic state together.

According to known / 7 processes for generating hydrogen from water, hydrogen can be separated from water at ordinary temperatures by the action of highly electropositive metals or by electrolysis. Hydrogen can also be generated by reacting the hydrides of highly electropositive metals, such as LiH and CaH ₂ *, using water at ordinary temperatures. At higher temperatures, hydrogen can be separated from water by means of a few of the less electropositive metals and a few non-metals. Although some of these reactions are common for laboratory use, only one or two have been economically applied on a large scale *

The metals that can be used at higher temperatures, e.g. magnesium, manganese, zinc and iron, separate hydrogen from water do not separate at room temperature, but separate it when the metals are heated and the water is in the form of steam. The reaction these metals are produced with steam at higher temperatures

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Hydrogen gas and oxides rather than hydroxides of metals. If e.g. Steam is passed over heated magnesium, then the magnesium burns bright and solid magnesium oxide and hydrogen gas are produced:

(heated) (steam)

Mg + H ₂ O s> H ₂ ^ + MgO

and ^ H = - 86.0 Kcal / mol

Zinc, iron and manganese also react with steam when heated are, but less rapid than magnesium, with hydrogen gas and zinc oxide, iron oxide or manganese oxide being produced. All of those before The reactions mentioned are exothermic, so that once started they generally give off enough heat so that maintaining the high temperatures necessary for the reaction to sustain itself to the extent necessary receives.

Certain non-metals, e.g. carbon, separate at high temperatures also hydrogen from water, whereby an oxide of the non-ferrous metal and hydrogen gas are produced, (heated) (steam)

C + H ₂ O ^ H ₂ I + CO

and JN ₁ H- + 31 * 4 Kcal / mol

This reaction is endothermic, so it is necessary to add heat to keep the reaction going.

The so-called Bosch process steam is passed through the incandescent coke of about 1000 ⁰ C, wherein a mixture of hydrogen and carbon

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fuel monoxide, so-called water gas, is generated. This is an endothermic reaction and a continuous supply of coke is required to maintain the temperatures essential for the reaction to maintain. The hot carbon acts as a reducing agent and removes the oxygen from the steam. Included When heat is consumed in the reaction, the temperature of the coke falls as the reaction proceeds, and hence becomes the reaction slows down and eventually ends the reaction. The coke must then be reheated if the formation of water gas continues shall be. This is completed in practice by the endothermic stage, the generation of water gas, is alternated with the exothermic stage of reheating the coke. As the coke is reheated, it is continuously consumed, the residue being removed and new coke being added and needs to be heated. When the coke is burned, a corresponding heat is developed to make the temperature red-hot Increase heat which can then react further with the steam to form a mixture of hydrogen and carbon monoxide to create.

In a variant of the Bosch process, Erelöi · hydrocarbons are used instead of coke. Improved reactions between hydrocarbons and steam in the presence of catalysts at very high temperatures (110O ⁰ C) produce a mixture of Hp and Co. The hydrocarbon methane reacts with the steam: (gas) (steam)

CH ₄ + H ₂ O ^ H ₂ ^ + CO

and AH- + 49.5 Kcal / mol ■

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This mixture of Hg gas and CO gas can be used as fuel. However, if hydrogen is the desired product, then the two gases must be separated by making the carbon monoxide gas in the presence of a catalyst with additional steam at a lower temperature (50 ° C) to react generate more hydrogen gas and carbon dioxide gas. These The two gases can be separated by passing the mixture through cold water under high pressure. The carbon dioxide gas dissolves and the hydrogen gas is collected above the water.

All known processes for producing hydrogen or a fuel gas containing hydrogen have a defect or failure. one disadvantage in common. In addition to water, all of these processes require a second consumption substance. The price for and availability via this second consumption substance an obstacle to the economic use of these known processes. Further are the procedures that may be are feasible on a larger scale, all cyclical in nature and cannot be operated continuously what renders them unsuitable for implementation on a larger scale.

Known process for the reconversion of iron oxide into his Original state (reconstitution) always consist in that Iron is reduced with one form or another of carbon. This carbon is e.g. in the form of coal, lignite, Coke, hydrocarbon, etc. before and the reduction requires extreme heat and pressures in order for the iron to return as before

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Generation of hydrogen is usable. This well-known process is self-defeating because of the introduction of carbon in iron under the conditions described causes a further reaction, which converts the iron into a carbon-steel alloy includes, which is not fully satisfactory for the production of hydrogen. Every cyclical pass of creating and reconstituting brings more carbon into the steel until the iron mass eventually becomes contaminated high-carbon steel is converted to act as a reactant is unusable for the steam-iron production of hydrogen. The addition of coal, lignite, coke, hydrocarbon and hydrogen introduces other impurities that are unacceptable.

It is therefore primarily an object of the invention to provide a method of the initially to create said type, which is free from the disadvantages associated with the known methods. The invention wants too create a process in which water is the only consumable substance is. Furthermore, the process to be created should be highly efficient. The process to be created should then be able to be carried out essentially continuously. Object of the invention it is also to create a device of the type mentioned at the beginning with which a method according to the invention can be carried out.

It is a further primary object of the invention to provide a method of the initially mentioned type in which the reactant is reconstitutable without contamination. It is also a task ₍ a method of non-contaminating reconstitution

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a reactant used in the production of hydrogen to accomplish. The invention also seeks to provide an apparatus suitable for carrying out this method. Then want the invention provide a method and apparatus with which or a metal oxide without the use of a contaminant Material is convertible into the corresponding metal or a lower oxide.

The invention provides a method according to claim 1. Independent The invention also provides a method according to the characterizing features of claim 6. The invention then provides a method for reducing metal oxide according to the characterizing features of the patent claim 13 before.

The invention also provides a device according to claim 15 before.

The invention also provides a pluidum control valve according to the characterizing Features of claim 2> before. The invention then provides a pluidum partial valve according to the characterizing Features of claim 25 before.

Thus, in a preferred embodiment of the invention Generation of hydrogen and the reconstitution of the reactant essentially continuously by adding a plurality of Reaction chambers is provided, a reaction agent is provided in each reaction chamber and the hydrogen generation steps is carried out in the first half of the reaction chambers, while in the other half of the reaction chambers

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Reagent is regenerated. So if hydrogen generation and reconstitution are performed alternately,

one
half of the reaction chambers is used for hydrogen generation and the other half for reactant regeneration. By means of suitable distribution means and suitable control means, the overall mode of operation of the method and the device essentially represents a continuous generation of hydrogen.

Before the device and the method according to the invention in detail There is a detailed discussion of the principles on which the method and apparatus are based based according to the invention. It has already been mentioned that the reactant used in the invention is a metal capable of is to exothermically separate hydrogen from water with the formation of an oxide of the metal, and the oxide of which is capable in the To spontaneously dissociate or disproportionate in the absence of free oxygen. It is to be kept in mind that although this is comprehensive Definition of the reactant is, it will be readily understood by those skilled in the art that this does not mean that these reactions must take place at room temperature, it just means that these reactions take place at any practically achievable temperature can take place. So in order to set the hydrogen production process in motion, the reactant is adjusted to the temperature heated, during which it separates hydrogen from water exothermically and water is passed over the reactant. There the reaction is exothermic, it is self-sustaining.

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According to the invention, the initial heating is carried out, for example, by electrical means Resistance heating. There is, of course, a practical aspect of which metal is used in the invention is advantageous, and which consists in the fact that the temperature at which the metal separates hydrogen from water exothermically, and the temperature at which the metal oxide spontaneously dissociates or disproportionates, generally below the melting point of the metal should lie so that the practical problems associated with the maintenance of the reactant and the reaction are easily detachable. This does not mean that the use of a molten reactant in the future is also out of the question can be drawn.

In view of the aforementioned practical requirement, it arises Surprisingly, that two metals, in the form of pure metals or of oxides of low oxidation state which have important physical properties that are required by a reactant for the practical use of the invention are required; therefore, these two metals are preferred reactants. These two metals are manganese and iron and compounds of manganese and iron. The reactants represent in a process according to the invention represent a type of catalyst and could also be referred to as catalysts.

Manganese occurs in many oxidic ores, the most important of which is pyrolusite MnOp, a black mineral. Ores of less importance are Braunite Mn ₃ O ,, Manganese! T Mn ₃ O, .HpO and Hausmanit MnO.MtuO, · Manganese is also rich in many clays and shale clays.

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borrowed existing impurity and present in most iron ores. As such, metallic manganese is not widely used in industry. However, an iron-manganese alloy called perromanganese, which contains 75 to 80 % manganese, is widely used in the manufacture of special steel. The addition of small amounts of ferromanganese improves the quality of steel by removing traces of oxygen and sulfur through the formation of MnOp and MnS, which are secreted by the steel into the slag. The addition of larger quantities of ferromanganese results in steel of great hardness.

Iron is the fourth most abundant element in the earth's crust and the second most abundant metal after aluminum. In nature, iron occurs only in chemical compounds, principally as an oxide or carbonate, and less frequently as a sulphide. The main ores are hematite Fe ₃ O ,, magnetite FeO.Fe ₂ O, and hydrogenated iron oxide, so-called limonite Fe ₂ O, .XH ₂ O. The main carbonate ore is siderite FeCO ^. The main sulphide ore iron pyrite FeSg. Pure iron is rarely used in industry; but steel, which is an alloy of iron with other metals and contains very low percentages of carbon, is used in enormous amounts.

The two metals manganese and iron are among the eight elements that make up the first transition series of elements. the first transition series, the transition metals and their physical properties will now be discussed.

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In a very general environmental environment, all transition metals are solid Metals of usually white or light gray color that can be polished to a brilliant state. Lots of transition elements occur in more than one crystalline form; For example, iron exists in a densely packed cubic shape or in a body-centered cubic shape, depending on the thermal conditions it was subjected to during crystallization is, and according to the impurities present. The transition metals are hard, malleable and ductile, and excellent mechanical properties.

The transition metals have a relatively high density and very high melting and boiling points and a high heat of atomization. These Properties show that the atoms of these elements are held together by very strong metallic bonds, even in the remain solid in the molten state. The strength of the bond between metal atoms depends on the interaction of the electrons in the outermost shell of the atoms. The valent electrons are responsible for the bond, and the greater the number of valent electrons, the stronger the resulting bond. The atoms of the transition elements have three or more Electrons that are available for interaction and at least one of these electrons is a d electron; consequently the interatomic bond is very strong.

Since the electron configurations of successive elements of the first transition series are only separated by one electron in the distinguish between the third electron shell, there are only slight

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differences in the ionization energies of neighboring elements, differences that are not nearly as great as those between successive elements in a non-transition series.

The following should be noted about the chemical properties and oxidation states of transition metals: All transition elements with the exception of scandium and the heavier elements of group III A (ytterium and lanthanum) show a different oxidation state. Scandium shows only one oxidation state, + J, but each of the other elements of the first transition series has two or more oxidation states, which vary from the positive value, that of the period group number of the element to lower positive values and finally to zero or even to the negative ones Values - 1 and - 2 extend, in the highest oxidation states + 5 * +6 and + 7 the transition elements form complex anions with oxide ions, 0 ", as ligants. In the case of complex oxo anions, the metal-oxygen bond has a largely covalent character, The transition metals in the higher oxidation states resemble the non-metallic elements of the corresponding groups B. In the +2 and +3 oxidation states, the transition elements form essentially ionic compounds with most of the electronegative elements; the MO oxides, for example, are essentially ionic pollutants.

Electropositive character and reactivity are intertwined. As stated above, each element usually shows different possible oxidation levels and

-28-609 8 19/0968

J? ■ #.

each element at a given oxidation state is characterized by a different set of physical properties, e.g. by a certain value of the charge-radius ratio, a certain preferred number of coordinates and stereochemistry, by a certain oxidation-reduction potential, etc. However, all of the different characteristics between the transition elements in their various states can be logically related to the two main factors which, in general, are behavior determine all substances, namely the thermodynamic and the kinetic properties.

It should be made clear that the positively charged ions are the transition elements have a great tendency to form coordination compounds with virtually all electron pair donors, see above that their chemistry always includes the reaction of complex species. All elements of the first transition series are electropositive, like show their positive standard oxidation potentials according to standard tables, and form very stable oxides. At ordinary temperatures and especially in compact form, however, these metals are kinetically ineffective, since with their high heat of atomization a high activation energy. The degree to which the metal is divided, the type of particle surface and the thermal Treatment to which the metal was subjected during its preparation are usually factors that affect the kinetic Determine and influence the reactivity of these metals.

The elements of the first transition series form different oxides, which are represented by MO, M ₂ O ,, M-, 0 ^ or MO.MgO ,, MO ₂ MgO ^

-29- 609819/0968

and MO- *. Oxides of the + 2 - oxidation state are known for all elements of the series with the exception of Sc and Cr; the divalent oxides MO have a crystal lattice of the NaCl type, each M ⁺⁺ ion is octahedral surrounded by six O = ions and every 0 - / 'octahedral is surrounded by six M ⁺⁺ ions. Oxides of the +3 oxidation state, M ₂ O- *, are known for all elements of the series with the exception of Co and Ni; these oxides have lattices,

+3 -

in which every M ion is octahedrally surrounded by snchs O ¹ "ions, while every 0 ~ ion is surrounded tetrahedrally by four M ions. Oxides of the +4 oxidation state, MOp, are known for Ti, V and Mn; they have the rutile structure with a 6: 3 cation-to-anion crystal coordination.Oxides of the formula M ^ Oh or MO.M ₂ O ^ contain one third of the metal atoms in the +2 oxidation state and two thirds in the +3 oxidation state. The structure of these oxides consists of ionic lattices in which M ⁺⁺ ions, M ions and 0 ⁼ ions alternate in various regular patterns.

Thermodynamic calculations are generally performed using a wide range of temperatures performed with algebraic equations representing the characteristic properties of the straight represent the substances under consideration. The necessary integrations and differentiations or other mathematical treatments can then usually be carried out easily. Most of the time The usual starting point for performing such calculations for a given substance is the heat capacity at constant Pressure. From this size and the knowledge of the properties of any phase transitions, the other

-30- ■ 609819/0968

if.

³ ^ "2R49-370

their thermodynamic properties by known equations, which are given in common texts of thermodynamics ^^^.

Empirical heat capacity equations generally take the form of an energy series with independent variables. Cp = a + (b'x 10 "x ⁵ ) T + (c'x 10" ⁶ ) T ² or

Cp - a " ₊ (b" x 1 (T ³ ) T

since both forms are used:

(1) Cp = a + (b χ 10 "^) T + (c χ 10 ~ ⁶ ) T ² +

The constants a, b, c and d can be experimental or passed determine a valid theoretical or semi-empirical approximation. The heat content or the enthalpy H is derived from the heat capacity calculated by a simple integration over the range of temperatures for which (1) is applicable.

Therefore if 298.0 K (Kelvin) is taken as the reference temperature

the following applies: T

(2) Ht - H ₂₉₈ - C CpdT

298
= a (T - 298) + 1/2 (b χ 1 (T ⁵ ) (T ² - 298 ² ) + 1/5 (c χ

ίο " ⁶ ) (τ ⁵ - 298 ^) - (d χ io ⁵ ) ( 1 - 255)

= a T + 1/2 (b χ 10 " ⁵ ) T ² + 1/5 (c χ 10 ~ ⁶ ) T ³ - -A

where all the constants on the right-hand side of the equation are summarized in the expression -A.

609819/0968

so

In general, the enthalpy is given by a sum of expressions according to (2) given for substance phases of the temperature range under consideration, plus expressions which the transition

represent heat:

^T 2

^T l

, M) In a similar way, the entropy S from is obtained by performing integration

ß) ³ T ' ^S 298

= aln- ( ^T / 298) + (bxio " ³ ) (T-298) + 1/2 (c χ 1θ" ⁶ ) (T ² -298 ² ) -

1/2 (d χ 10 ⁵ ) (-4- 5—

τ 298 ^

- aln T + (b χ 1θ " ³ ) T + 1/2 (c χ 1O ~ ⁶ ) T - Β 'or (4) s = ^a 2.503a log T + (b χ 10 * - ⁵ ) T + 1 / 2 (c χ 10)

φ 1/2 (dx 10 ³ ) -,

_T _ _B

whereby

(?) ^{B = B} '- ^S 298

from the definition of the free energy G:

G = H - TS
the amount

609819/0968

is obtained from (2) and (4):

(6) G _T -H ₂₉ 8 ⁼ ~ ² ^ ° \ ^T log ^T " ^1/2 < ^{bx 1O} " ³ > T ² -1/6 (c χ

10 ~ ⁶ ) T ³ - 1/2) + (B + a) T + A and also the free energy function

(7) G - H ₂₉₈ = -2.303 _a log T-1/2 (b χ 1θ " ³ ) T-1/6 (c χ 1θ" ⁶ )

_T 2 . _1/2

_{(B + a)} . _A

Table 1
Educational levels in (Kcal / n ^ !.) of manganese and iron oxides

MO -92-64

M ₂ O ₅ -229 -197

M ₅ O ^ -331 -268

MO ₀ -124

-33-609819 / 0 968

T.T.TC 2

Heat of formation (coefficients: free energy equations)

A. The Ah values in grams of calories per mole

B. The a, b, and I values listed here are used to calculate the, / ^ G- and using the following equations: Jsß _t = ^ H ₀ + 2.303 _a T log T + b χ 10 " ⁵ T ² + ex 10 ⁵ T "+ IT reference: Bulletin 542

/, S = -a - 2.303 log T - 2b χ

J- · Jj SL

+ c χ 10 ⁵ Τ " ² - I

Bureau of Mines
United States

Valid Reaction O ₂ (ε) and temperature range: (298.16 ° -373.16 ° K): ί -7Θ.6ΟΟ s 2,3o3 _a :
I.
i ι
I.
b: <
c: I.
I ^:
: I. H ₂ (g) + 1/2 O ₂ (g) = H ₂ O (I) (298.16 ° -2000 ⁰ K) · ! -56,930: ' -18.26: -0.64: . -0.08: ί -8.74 H ₂ (g) + 1/2 - H ₂ O (g) 4th
4th + 6.75 s « I.
i ! +93.59 + 1 / 2O ₂ iron _g47 0 (c) (298.16 ° - s
^y '1.033 κ) ! -65,320! *
r 1 I. I.
t I 0.947 P _e (*) ^{+ 1/2} ° 2 M = ^p e0, Q ₄ y0 (c) (ΐ $ 033—:
^y '1,179 K) ί -62,380 i I.
-11.26: : +2.61: t i
t i ^! +43.60 0.947 pg (P) ♦ VSO ₂ («) - ^F .o, w ^{0 (0) (} iÄ ·. -66,750 "' i + 4.08 i : -0.75! ¹ '
ί + 0.23S \ + 3.00 0.947 ρ
e Ci) + 1 / 2O ₂ <«>" ^P .o. I.
ί -64,200 : -8.04 - : +0.67 i -0.10 • +42.28 0.947 Fg (r) + 1 / 2O ₂ ^{s > = ^p _e o. I -59,650 Ί -18.72 <
i +1.67 \ -0.10 ί +73.45 0.947 pg U) + 1 / 2O ₂ : -63,660 I.
I -6.84 : +0.25 ί -0.10 ! +34.81 0.947 pg Ct) (g) = P
VO / ·> ■ gQ ί -7.48 ! +0.25 ί-0.10 ί +39.12

CD CD (O

Valid response and d ^) + 20g (g) - P ₆₅ O ₄ ( Temperature range; .033 ° K) '-272 • ² P ⁰ V + 1 b : c: I. , 52 [Iron] magnetite l \ ) +20 ₂ (g) = P _e3 0 ₄ ( 1,179 ° K) : -262 : : +1 : 19th 5P _e ( j) + 2O ₂ (E) - P ₆₃ O ₄ K 6) (900 ° - ! -276 • 500: -54.27: +5 1.65 : +0.245: +255 , 52 5P _e ( ί) + 2O ₂ (E) = P ₆₃ O ₄ ( ß) $ 1.055 ° - .803 ⁰ K) ί -262 .990: -5.71: +1 , 00 : -0.40: +89, o5 3P _e ( Bisen P (1,179 ° - • 990: -44.05: .50 : -0.40: +215 5P _e (i i) + 2O ₂ (E) - PeAi / J) (1,674 ° - .874 ⁰ K) ί 275. 56θ: -6.40: + 1 , 00 : -0.40: +91, , 84 : : :: 5P _e ( A) (1,803 ° - 280: -8.74: , 00 : -0.4: +104 -1 -1 -1

5P ₆ (P + 2O ₂ (g)

(I.874

2,000 ° K): -257,240 -26.89: +1.00: * 0.4: +155.46

hematite

2P.

(298.16

95O ° K)

2P.

(950

1,055 ° K)

-200,000

-202,960

-15.84: -1.45: -1.905: +108.26

-42.64: +7.85: -0.15: + 188.48

2P.

(1,035 ° 1,050 ° K)

196.740

-10.27: +0.75: -0.50: +92.26

2P _e (ft) + 5 / 2O ₂ (gH

(γ) (i.05o ° -1.179 ⁰ K)

-195 200

-0.39: -0.13: -0.30: +59.96

2P ₆ (Y) + 5 / 2O ₂ (E) = P ₆₂ O, (γ) (1,179 '- 1,674 ^U K)

-202,540

-25.95: +2.87: -0.30: +142.85

-2-

CF) ο co 00

co

O CD σ> oo

2P _e (S) +3/20 ₂ (g) = P _e2 ° 5 (T) (1.674 ° 1.80O ⁰ K): -192-920: -0.85: -0.1? : -0.30: +61.21

manganese

_n (&.) + 1 / 2O ₂ (g) = M _n O (c) (298.16 ° 1,000 ° K): -92,600: -4.21: +0.97: +0.155: +29.66

M _n (λ) + 1/20 ₂ (g) - Μ _β 0 (c) (1; 000 ° 1 374 ° Κ): -91 900: +1.84: -0.39: +0, 34: +12.15

M _n

+ 1/20 ₂ (g) = M _n 0 (c) (I.374 ⁰ 1.41O ° K): -89.810: +7.30: -0.72: +0.34: -6.05

cn

--F-CD CO -J

-3-

Valid response and a) manganese Temperature range 517 ⁰ K) •
0 •
* 2 _; 303 _a : b : G 34 : I. (M + 1 / 2O ₂ (S) = M _n O ( 000 ⁰ K) 34 "n .. + 1 / 2O ₂ (S) = M _n 0 ( c) (1.410 1. : -89. 390: +8 _; 68: -0, 72: +0, : -10.70 M. 3M _n '( χ 000 ⁰ K) : -93. 350: +7.99: -0, 72: +0, 145 : -5.9o ) +20 ₂ (g) = M _n3 0 ₄ - : -332 .400: -7.41: +0, 66: +0, : +106.62 «0 (298.16 ° 1.

Jt in

· » O

CVl

Jt

IA
ί-Ο

ΙΛ

ΙΛ

O*

Jt

CU O CU

LA

O O

Jt

•1

Jt

CU

T- CU

O O O

t CU ΙΛ

ο *

CU O CU

sf

J?

• I

Jt

O O

Jt

CU

O O

co

OJ

CVJ KN.

O O

Jt

to

CU O CU

«Λ)

O CU

IA CJN

O O

IA

O OO

co

CXl

IA

O IA

CU

O VO

Ο «O O

CU O CU

» O O KN O 1- LA ¹ N LA O Jt O O t- KN O O VO O T- O C. Jt O O O O LfN CJN * 5
T O τ- ON O O co LA O KN LA LA T LA IA T- T- • LA -Φ VO τ- K \ τ— KN τ— KN O LA ON T- KN rl T- "» - ^ τ- Ο LA O O ^{+ + +} T ~ O ⁺ 09 + O O ΙΑ ⁺ VO VO σ \ OO ^Sw ' τ- O CU KN KN «I. T- ON ·, * - ' KN O KN O KN • 4 co O CU I. I. I. x-> O ON ¹ O I. vo CU »Γ O '+ CU "" κ \ O Il OO H VO O LA • ι ·, KN τ- σ \ CU τ— On S. OO O VO Φι ■ Ρ «I. + CU τ- CU IA
ι Il VO O O Ο O O oo CU O O KN O CU T- Γ O O S. O + 3 / CU ■ + T- O VO CU CU LA 2 CU 3 π Q O σ \ CU if CU V.M KN CU VO ^> ΙΛ .cu CU CU CU CU O CU 3 CU ΙΛ CU ¹ I. I. τ- CU I. S. I. »· ■ ·«. KN Ι O CU + "w O ( CU
ε
«U O a U
T K
T O O O O τ— * ~ ^ C. KN O Ir CU O CU + 3 / G CU

609819/0968

TABLE 3

A. The first column gives the elements or oxides, the second column the phase on which the data are referenced are applicable. The third, fourth and fifth columns specify the thermodynamic Properties for the transition to the next phase. In the sixth column the entropy value is given at the reference temperature of 298.16 K. The remaining columns with the exception the latter give the values of the constants a, b, c, d, A and B that make up the thermodynamic equation required are.

B. All values in the table that represent estimates are in brackets.

C. The heat capacities of temperatures beyond the range of experimental determination will be estimated based on extrapolation.

(O 00

co ■ «^ CD CD (J) CO

Element: Phase: Tempera-:
or:: door of:
Oxydf>:: Transi-:
:: tion ^u K: Warmth of:
Transi
tion:
Kcal / mol. ι Entropy:
! Transi-:
s tion:
: (eu): -Entropy:
298 ⁰ K:
: (eu): a:
I.
I.
4th : b: I.
I.
c:
I.
i
► 1
► 4 . d: AB
: Kcal /: Kcal /
: mol: mol H ₂ O (g): gaseous: j ! 45.11: 11.2 i 7.17: I.
»4 ί: (3, ö58) :( 53.5) H ₂ O (JU: liquid: 373.16: 9.770 s 26.10: ί 16,716 s 8.2 i (0.4): * 4
»4 i- (0.2) :-( 49.67) - (20.2J P _Ä (S): fixed α: 1,033 s • 0.41 : 0.397! ί 6,491 y : 3.37: 7.10: : 0.43 :: 1.176: 14.59 Ρ _β (S): fixed: 1.1Ö0: : 0.217: 0.104 : 10.40: 1 ! : 4,201: 55.66 P _e (S): fixed γ: 1,673 J. : 0.15: 0.084 : 4.05: 3.00: ■
I. s: 0.396: 19.76 P _-1 (S): solid c; 1.Ö0Ö: ! 3.06: 2.14 t 4
I 4 ί 10.30: * :: 4.382: 55.11 P ο (sy : rest: 1.641: ! 7.5: 4.6 ι 12.9! ; 9.27: 4.8θ :: (2,977) :( 43.8) F _e , 6 ₄ (S) fixed: 900 i 35.0 ί 12.3b: 1.62 : -0.38: (3.826):, (: 58.3) P _e2 0, (s): fixed α. : 950 ί 0.16: 0.17 : 21.5

το cn

CD

CO

O *

0 «

-2-

Element: Phase: Tempera-: Warmth of: Entropy: Entrgpie:

the:: door of the: Transi-: Transi-: 298 K:

Oxyd ^:: Transi-: tion: tion::

:: tion (K): Kcal / mol: (e.u.): (e.u.):

d :: A: B
: Kcal /: Kcal /
: mol: mol

): fes1 ^: 1.050

: 21.88: 48.20:

: 8,666: (104.0)

cn o co

«N (S) : fixed $: ):fixed 1,900 ι 0.535 i ί 0.535! ^: : 5.70 ! 3.38: I 4
I. : -0.37 : 1,974 y 26.11 ^M n Cs) : fixed: 1,374 i 0.545! 0.397 ι ·
t ö, 33 : 0.66 : 2,672 j 41.02 M _n (S) : festy: 1,410 ί 0.430: ι 0.305 y ι ·
»· 10.70: ι : 4.76! : 56.84 W _n (S), : fixed ^: 1,517 ί 3.5! : 2.31 ι 11.30! : 5.176! 60.88 14.27: ■ M _n O (S) :fixed : 2.o5ö! ί 13.0! . 6.32! ί 35.5 11.11! : 1.94 : I.
I. ι -0.80 : 3,689 i ί 50.10 ^M n3 ) :fixed" : 1.44 $ « ί 4.97 yrs • 3.44: : 34.64 ι 10.02 ) 4
ft 4 ί -2.20 : 11,312: ! 166.30 M _n -J O ₄ (S): fixed $ : 1.Ö63 ι (33) j L (1ö) ι ί 26.4 : 50.20 ι
I. ι : 17,376 : 260.40 "112 O ₅ (p : Resolution s
1,620! ι <
ι 4 ί 12.7 : 2 4.73
•
• · ί 8.38 ft
ft
ι ί -3.23 : Ö, Ö29!
• 4
• : 118.80 M _n O ₂ (S) : fixed: resolution!
:: 1.120 4th : 16.60
• : 2.44
k ί -3.88 : 6.359. : 4.80 ι ·
»·
• ί 7.59

Reference: US Atomic Energy Commission Report: ANL-5750

TABLE 4 Values of chemical thermodynamic properties

Reference: National Bureau of Standards

500 - Selected Values, Chemical, Thermodynamics Properties.

Note: All values in Kcal per gram mol

substance State A ^H form A ^G form S ° •
• 12.9 • 35.5 F _e G : 96.68 : 85.76 21.5 F _Ä 0: S. : - 63.7 : - 58.4: 35.0 ^F e2 ° 3 ^: S. : -196.5 : -177.1: 45.11 ^P e3 ° 4 ^: S. : -267.0 : -242.4: 16.72 M _n G : 68.34 : 58.23: 14.4 12.7 M _n O S. : - 92.0 : - Ö6,8: M _n O ₂ S. : -124.5 : -111.4: ^M n2 ° 3 ^: S. : -232.1 • ·
• · ^M n3 ° 4 ' S. : -331.4 : - 306.0: H ₂ O: G : - 57.80 : - 54.64: H ₂ O: 1 : - 68.32 : - 56.69:

609819/0968

254937Q 39

TABLE 5

Physical constant

Reference: Bureau of Mines Bulletin

Element or: Molecular: Density: Melting * Boiling: Specific Oxide: weight: gravity: point (° c): point: heat (25 ° c

TO Ccal / g

: 55.847 : 7.86 ν c; c _p = cal / g ^P e : 1,535.0: 3,000: 0, 106 : 159.69 : 5.24 ^P e2 ° 3 : 71.85 : 5.7 : 1,565.0:: ^P e ° • : 1,420.0:: : 54.938 : 7.2 «N : 1,244.0: 2,097: 0, 114 : 70.94 : 5.44 M _n O : 157.87 : 4.5 φ φ ■ «N2 ° 3 : 228.81 : 4.856 : (-0) 1.Ο8θ:: «N3 ° 4 : 86.94 : 5.026 : 1,705:: «N ^O 2 : (- 0) 535::

609819/0968

2 5 4 9 3 7 ü HQ

Generation of hydrogen

2 Pe _{(g) +} 3H ₂ O _(g) > 3H

heats steam

1540.4 + 648.0 \ ⁷² > ⁷²

(Grams) (grams) (grams) (grams)

To the oxygen _; which has reacted to FepO ^ is to be determined ^ is subtracted 1915.68 - 1340.4 = 575.28 grams of oxygen. The equation shows that 72.72 grams of oxygen are produced.

Since hydrogen weighs 0.00531 x 453.59g per 0.02832 nr, i.e. the specific gravity of hydrogen is known, about 30.19 x 0.02832 irr (approximately 8.56 nr) of hydrogen are produced. The iron weighs originally 1340.4 g and now 1915.68 g, the additional weight being due to the oxygen present in the iron oxide Fe ₂ O now present. This amount of 575 * 28 g oxygen wa & now out of the iron oxide Fe ₂ O ^ be removed so that the production can be continued by hydrogen. When the oxygen is removed, the Fe ₂ O becomes Fe, which is exactly what is desired.

If the components of the reaction are considered in detail, it should be noted that the structure of iron is either in a dense cubic or in a body-centered form, depending on the thermal conditions to which it was subjected during its crystallization and the presence of Depends on impurities. This metal of the first transition series has a relatively high density, a high melting and boiling point and a very high heat of atomization. This proprietary

609819/0968

Shafts make it clear that iron atoms are held together by very strong metallic bonds that withstand when molten. As stated earlier, atoms of iron in the molten state have three or more electrons available for interaction _/ and the presence of these electrons makes the interatomic bond very strong.

The gaseous oxygen molecule Op is a diatomic molecule, in which the two oxygen atoms are a pair of electrons in a sigma bond electron shell and another pair of Share electrons in a pi-bond electron shell '; every oxygen atom so has two separate pairs of electrons.

Finally, iron oxide FepO ^ is thermodynamically stable against decomposition into metal and oxygen gas at ordinary temperatures. Oxides of the same metal exhibiting different oxidation states have different relative stabilities and consequently the ability to partially dissociate or disproportionate; however, these processes do not take place to any detectable extent at ordinary temperatures. For example, of the two oxides FepO and FeO ₂ , the former is the more stable at room temperature.

The thermodynamically impermissible reaction:

2Fe, 0. + 1/2 Op> 3Fe _p 0, Δ ^H ° * "55 kcal / mol-eqn

*> *? £ S = - 46 kcal / mol-eqn

609819/0968

does not take place at room temperature because the activation energy is too high.

Step one- atomization of ferrous metal (bond breaking) ^ atomiz - + 99 * 7 Κ / cal mol at 25 ° C and 1 atm.

+ 99.7 x 2 (mol) = 199 * 4 Kcal / mol eqn.

Step two - dissociation of oxygen molecules (bond breaking)

2 (g)> ²

^{= +} x 6 = + 357.6 Kcal / mol eqn.

Step three - ionization of each iron atom Pe _(g) -> Fe + + _(g) +

A ^H ioni _Z ^{= Fe} (g) -> ^{Pe ++} (g) +25:

A ^H ioniz ^{= + 2} 61, O x ² (mol) = 522.0 Kcal / mol eqn. This represents the sum of the first and second ionization energies of iron.
Step four - reaction of each oxygen atom

iS ^H electron affinity = ⁺ ^ ⁶ ^ Keal / mol 0 _(g) atoms A ^H electron affinity = ¹ * ^15β ' ^{9 x 5} < ^mo1 ) ^{= + 468} ' ⁹ Kcal / mol eqn. Step five - reaction of Pe ⁺⁺ (g) with CT (g) to form ionic pesticides (bond formation)

^ ^H bond formation- " ¹⁹⁴¹ ^ Kcal / mol eqn then: - 19 * 1.9 + (+ 199.4 + 557.6 + 522.0 + 468.9>

- - 1941.9 + 1547.9

- - 394 Kcal / formula = - 197 Kcal / mol

6098 19/0968

For a graph of the enthalpy of the reaction reference is made to Pig.1.

Reduction of iron oxide using hydrogen

Usually the oxide is reduced by hydrogen: (heated)

> 2 Pe +

(1915.68) (72.72) (1340.4) (648.0) Gram gram gram gram

This equation shows the well-known fact that iron oxide can be reduced by hydrogen when it is in an atmosphere this gas is heated. The equation also shows the fact that this is a common method of reducing metal oxides may not be of economic interest because when this procedure is fully carried out, this procedure requires every gram of hydrogen previously produced with the same iron heated and exposed to steam is.

According to the invention it has now been found that iron oxide at temperatures has an increasing tendency to dissociate above 1000 C, and does so, if not a considerable amount is made available by oxygen in its environmental environment. In other words, if from the environmental environment all oxygen is eliminated, then dissociated or disproportionate

ο iron oxide at temperatures above 1000 C up to a point,

6098 1 9/0968

in which the oxidation level has decreased, so that the process can be repeated without diminishing the action or response.

It has also been found that when the oxygen content in the surrounding atmosphere is restricted, steam is a very has a strong reducing effect on iron oxides. A review These reactions in the thermodynamic field show that the J ^ G values of the formation of water vapor at all temperatures are considerably more negative than those of the change:

4Pe ^ O ₄ + O ₂ γ 6 Fe ₂ OJ

and are also more negative than those of the change:

6 Fe 0 + O ₂ -> 2 Fe O ^

The reduction of iron oxide with water can therefore be predicted even under specific conditions.

The successive reduction of iron oxides can be represented by the following equations:
6 Fe ₂ O ^ - Op ■ = 4 Pe O ₁ , = 4 Pe 0.4 Fe ₂ O, 2 Fe ₂ O, - Op ^ 4 Fe 0
2 Pe 0 - O ₂ - 2 Fe

It is also important to note that when the oxides of manganese are heated to high temperatures, these oxides dissociate while releasing part of their bound oxygen, forming an oxide with a lower oxidation number.

1) The manganese oxide MnO ₂ releases part of its bound oxygen at 535 ° C and reduces to Mn ₃ O ,.

2) The manganese oxide Mn ₂ O, releases part of its oxygen at 1080 ° C and reduces to 2MnO.

609819/0968

This dissociation of oxygen is achieved by the action of heat alone; however, the building material must be removed immediately in order to prevent it from recombining with the 2MnO, which increases the oxidation number and finally 2MnO again _? or even Mn-O ₂ , is present.

This kind of decomposition occurs only in the case of oxides of elements which have different oxidation numbers; the choice of iron and Manganese as the preferred metals of the invention occurs because of this particular physical property as well as because of the fact that these two metals are among the very few metals that have the ability to separate hydrogen from steam, when the metals are heated to a minimum of red heat. This reaction is exothermic and self-sustaining. Another important one A consideration in the practical selection of these two elements is that they are both readily available and economically useful are.

When one of the two metals is machined on a turntable in this way is that it forms a very heavy thread to subject a maximum of surface area to the reaction, then it reacts very strong in the manner described. "Leave the two metals also alloy with each other to varying degrees, after which they act in a way that corresponds to the percentage of each in the metal contained in the alloy is directly proportional.

Because the oxides dissociate into their elements at temperatures over 1000 ° C occurs to an increasing extent and since these oxides

6098 19/0968

■ If ■

If their melting points do not reach temperatures below 15 ² K) C for iron oxide and 1705 C for manganese oxide, these oxides are treated at working temperatures, atmospheric times and times, which then initiate and complete reductions in the oxidation number solely due to heat-related dissociation. The presence of water during this period actually lowers the temperatures required to complete the reduction.

More facts about oxygen:

1) The radius of the O "-lon (1.32 $) is roughly equal to that of the Fe ion (1-33 S). In general, the compounds with the highest lattice energy are the compounds with small divalent and trivalent ions, e.g. Mg ⁺⁺ and Al ⁺⁺⁺ , and then with relatively small divalent anions, such as the oxide ion 0 ".

2) Oxygen gas is a little heavier than air. It owns a Density of 1.429 S per liter, measured at 0 C and 1 atm pressure, whereas the average density of air is about 1.30 g per liter under the same conditions.

3) oxygen is slightly paramagnetic; i.e. it is physically attracted to a magnet like a piece of iron, whereby the magnetic effect is valuable even when the molecules are far apart.

With regard to the stability of connections, it should be noted that that a given compound, under specific temperature and pressure conditions, does not have the ability to convert into its elements decayed, and carefully of any substance that is considered

609819/0968

a possible reaction agent could act, is kept away, but has the ability to disintegrate by entering into reactions through or with itself. z.I ^ is the connection a disintegration into different compounds, a disproportionation (self-oxidation-reduction) or subjected to polymerization.

For example, the decomposition of solid potassium chlorate into solid potassium chloride and oxygen at 25 ° C is considered. From the thermodynamic tables one can see for the reaction Λ H ° _f and S °:

³ (s) ^{(s) 2} (g)

are Ali £ _orm (Kcal / mol) - 93.5 - 104.2 O and S ° (cal / mol χ degrees K): + 34.2 + 19.8 3/2 (+49.0) and then do the math :

° = - 104.2 - (- 93.5) = -10.7 Kcal / mol eqn * = 3/2 (49.0) + 19.8 - 34.2 = +59.1 cal / mol eqn χ Degree T As ⁰ - 298 degree χ (+59.1) cal / mol χ degree = + 17.7 Kcal / mol-eqn G ° =

Λδ ° = -10.7 - (+17.7) - - 28.4 Kcal / mol-eqn

If you look at the decay of KClO-, into its elements in their state

ard conditions at 25 ° C:

KClO, ^ K / _O x + 1/2 Cl ₀ + 3/2

considered, then one finds by comparison and following the procedure outlined above that:
⁰ = + 63.3 Kcal / mol-eqn

60981 9/0968

One can conclude that KClO, can not spontaneously decompose into its elements at 25 ⁰ C and 1 atm, but that it has the ability to disintegrate in KCl f "\ _o and0. Indeed, pure crumbles

KClO ^ * and O ₀ , before the temperature is significantly above room ^{3 /} - ^{N 2} (g)

temperature is increased, and. Ewar, because of the ones necessary for this reaction high activation energy.

With regard to disproportionation, hydrogen peroxide is considered in the gaseous state. From data tables it can be seen that the free energy of the formation of H ₀ O ₀ at 25 ° C

(G)

and 1 atm is negative (G- = - 24.5 Kcal / mol H ₂ O ₀ ), so that

(g) H ₀ O ₀ does not decompose _{into H 0} and O ₀ under these conditions.

^{2 2} (g) ² (g) ² (g)

can fall. However, since the disproportionation of H ₀ O ₀ to HpO / ν Λ G ° is negative, it is suitable for the following reaction:

H ₂ O ₂ > H _o 0, ^ + 1/2

> p / p (g) ^{2 (g) 2} (g)

JS H ° _orm (Kcal / mol): - 52.5 - 57.8 0

S ° (cal / mol χ degrees K): + 54.2 + 45.1 + 1/2 (49.0) therefore / ^ H ⁰ = - 57.8 - 52.2 = - 25.6 Kcal / mol -eqn and

VS ° - 45.1 + 24.5 - 54.2 - + 15.4 cal / mol-eqn χ degrees T ^ S = 298 degrees χ (+15.4) cal mol-eqn χ degrees = + 4, 6 Kcal mol-eqn ^ G ⁰ - btt -T ^ S ° = - 25.5 - (+ 4.6) = - 50.2 Kcal mol-eqn HpOp, the disproportionation in H ₀ Oy ν and 0 /% suffer.

χ not in KCl x

609819/0968

With regard to spontaneous reactions, the guiding principle for deciding whether a physical or chemical transformation can occur spontaneously at a constant temperature and constant pressure: All systems strive to change from a state of higher free energy to a state of lower free energy. Therefore, a system can spontaneously transition from its initial state to its final state if the transformation involves a decrease in the free energy of the system (j \ g is negative). In other words: A system transformation tends to take place spontaneously in the direction that brings the system into a state of minimal free energy. Since the change in free energy at constant temperature and constant pressure is given by the expression £. G = JS ₁ H - TÄS is given, the ability of a given system to carry out a spontaneous transformation depends on two independent energy quantities, namely the Λ H energy quantity and the T / ^ S energy quantity, which are related to the one under consideration Conversions have their own signs and values:

1) A negative value of J ^ H (exothermic) is favorable to spontaneity. The TAS expression is preceded by a minus sign in the expression Ag = J ^ HT Λ S;

2) A positive W-type of ßß (disturbance reaction) is favorable to spontaneity. (T, the absolute temperature, is always positive. Summary:

AH -TAS Λ

Jexotherm-AH negative = favorable for spontaneous (. Reaction tanity

Λη (enthalpy value W

/ J endothermic <_H positive - unfavorable for I reaction spontaneity

6U98 19/0968

so

2 5 4 9 3 7 Π

/ disorder- «_ \ s positive ^ favorable for spontaneous reaction did

_ S (entropy value J.

^ Ordnungs- / JS negative = unfavorable for spontaneous reaction did

Hence, the actual value of UiG depends on a given conversion at constant temperature and constant pressure on the respective values of the Ah and T As energy expressions.

In view of the foregoing, the dissociation becomes solid Calcium carbonate in, solid calcium oxide and carbon dioxide gas considered at 25 C:

I AH ° = + 42.5 Kcal / mol-eqn

CaCo, -> CaOv ν + CO ₀ /

³ (s) ^{(S) 2} (g) ⁽ ]

\ T Λβ = + 11.5 Kcal / raol-eqn

It is obvious that this is an endothermic reaction because the value of the unfavorable <\ H -energy expression is greater than that of the favorable T / \ S energy expression, so that their difference is positive.

^ G ° = / \ H ° - T hs ° - = 42.5 - 11.5 - + 51 Kcal / mol-eqn This particular reaction is therefore thermodynamically forbidden at the specified temperature (unfavorable in terms of energy) and

O
does not follow, as is known, spontaneously at 25 C.

The temperature has an influence on the C G of a reaction. From the foregoing, it is readily understood that the value of the change in free energy, JS. G, and thus the ability of the reaction to proceed spontaneously, depends to a large extent on the temperature at which the reaction takes place. The expression

609819/096 8

._. G = ^ H - T ^ S means that the value of the temperature actually affects the value of Λ G; namely, not only is the T J \ ß energy terminus directly proportional to the absolute temperature, but both /) H out and AS have a characteristic dependence.

If one now assumes that the values of deifenthalpy and entropy changes AH and Ms of a specific reaction do not change within a certain temperature range, then a change in the temperature at which the reaction takes place can break the equilibrium between the A H and TA S Change energy expressions, which can change both the size and sign of Ag. In other words: A reaction that is thermodynamically impermissible at a particular temperature and pressure (Λβ = positive) can be thermodynamically permissible at a higher temperature (^ G = negative).

For example, reference is made to the preceding statements, according to which the dissociation of calcium carbonate at 25 ° C is thermodynamic is impermissible, as can be seen from the following expression s

^ iG = ^ H - TjÖS = + ^ 1 Kcal / mol-eqn.
Experience has shown that at 1 atm CaCo, completely

< ^S > oO

dissociates to CaO / N and CO ₀ when the temperature is 1.098 K

^{(S) 2} (g)

achieved. This of course means that a temperature rise of 298 K to 1,098 ^{0 0} K increases the T £ S-energy expression to the extent that the favorable entropy change eventually outweighs the unfavorable enthalpy change and the dissociation

609819/0 9 68

25A937Q

of CaCO, a spontaneous reaction becomes: ⁵ (s)

CaCo_> CaO / x + CO ₀

³ ) > ^{(S) 2}

(G)

- + 40.05 Kcal / rnol-eqn Λ G = - 2.11 Kcal / mol-eqn

AH - + 287.2 - 152.9 + 9 ^. 25

S = + 22.2 + -9.5 + (+51.06)

AH _response = -247.15 - (-287.2) = + 40.05

60.6 - ( ₊ 22.2) = ₊ 38.4

T / \ S ■ = 1098 degrees χ (+ 38.4 cal / raol-eqn χ degrees) = 42.16 Kcal / mol-

i) G - Λ H - tAs - + 40.05 - (+ 42.16) ^ G = - 2.11 Kcal / mol-eqn

It is interesting that the jfa Η-energy of this reaction does not change very much with temperature between 25 C ( £ ü - + 42.5 Kcal / mol-eqn) and 825 ° C (1.098 ° 'K, where Λη = + 4θ, Ο Kcal / mol-eqn). The ΔS of the reaction has not changed noticeably either. The change from a thermodynamically inadmissible to a permissible reaction is therefore primarily the result of the effect of the absolute temperature T on the size of the T ^ S energy expression.

The following applies to reactions in which the entropy of the system increases (disturbance reaction): When the reaction cannot take place spontaneously at a given temperature because of a large unfavorable A Η value (endothermic), then makes an increase the favorable T.As factor is relatively more important to the temperature, pollich there is a special temperature, albeit high

60981 9/0968

SS *

is where the favorable TAS expression ends up being the unfavorable one AH expression predominates, so the reaction is thermodynamic is permissible.

Production of hydrogen using pure iron oxide is possible. As a member of the transition element family, iron shows a variety of oxidation states. At normal temperature and normal pressure, all of these oxides are fall into the metal and oxygen gas thermodynamically stable. Iron oxides of different oxidation states have different relative stabilities and, consequently, the ability to partially to dissociate or disproportionate. These reactions take place but not to a noticeable extent at ordinary temperature. In other words: the behavior of the metallic The element iron and its ionic solid compounds is largely determined by kinetic factors.

It is known that the reaction of iron and its oxides (at high temperatures) with steam produces hydrogen and this reaction the metal or metal oxide is further oxidized. This reaction is exothermic, so once started it is sufficient Gives off heat in order to maintain the high temperature required for the reaction to take place at the desired level Maintains dimensions. The data sources used are taken from the US Mines Bureau, Bulletin 542, US Atomic Energy Commission, report 5750 and National Bureau for Standard Publications.

609819/0968

Sf Jt

Reaction:

Λ Η ¹ · ⁰⁰ ? ° (Kcal / mol): formation

3 (-62.58) - 56.9 - 272.3 _{χ degrees} ).

3 (+12.9) +45.1 + 35.0 + 34.6

The Λ H and -A S of the above reaction can be calculated from these values :

^ H ¹ Ä ° tion -AH ¹ ^ VlT products) -Δη '«(·« «R · -

action means)

= - 272.3 - (-244.04) = - 28.26 Kcal / mol-eqn ο

- " ²⁸ > ²⁶ Kcal / mol-eqn

(good for spontaneity)

" ^s ( ^{for all} products) - S (for all reaction agents) = + 69.6 - (+83.8) = - 14.2 Cal-Mol-eqn χ degrees = 1,000 degrees χ (-14.2) = - 14.2 Kcal / mol-eqn

Ag. = ha - tj5s

■ = - 28.26 - (-14.2) - - 14.06 u ^ G = - 14.06 Kcal / mol-eqn

(good for spontaneity) (assuming a 2-minute cycle) Heat generated by exothermic reaction - 14.06 Kcal / mol-eqn

14, O6 χ 80 (mol) χ 30 (cycles) - 33-744.0 Kcal / h. = 133,896.19 BTlf / hour (BTU = British thermal unit)

6Ü981 9/0968

254937Π

Note:

(Assuming a 1 minute cycle) - 267,792.38 BTU / hr Thermal energy required for dissociation - III.6OO BTU / hour. Energy balance (2-minute cycle)

133,896.19 - 111,600- 22,296.19 BTU / hr. (Excess) Note that the whole reaction is exothermic, but leads to a decrease in entropy or a higher order in the system, The Δ H energy term is favorable for a spontaneous transformation (■ A H is negative), whereas the T 4S energy term is actually is unfavorable (TÄS is negative), i.e. the entropy S of the system decreases with the transition from the initial to the final state. In the present Case, the reaction is able to take place spontaneously, since the favorable ^ Η-expression the unfavorable T&S-energy expression predominates.

Production of hydrogen using manganese oxides is also possible. Oxides of manganese are similar to oxides of iron in that they also form a number of oxidation states of varying stabilities and also have the ability to dissociate (or disproportionate). For the response:.

β _{Hn (s)} + ₉ H ₂ 0 _(g) --1W ^ 3 _M n ₂ 0 _{3 (s) +} 9 H ₂ ^

^ foäf (Kcal / mol):

0 9 (-56.9) 3 (-224.5) 0 β ¹ ' ⁴⁰⁰ (cal / mol χ degrees):

609819/09 68

6 (+8,827) 9 (+ 45, i). 3 (+26.4) ₉ ( ₊₅ 4.97) ^: "" ^6l 3> ⁵ - (-512.1) = - 161.4 Kcal / mol-eqn

: - - 161.4 Kcal / mol-eqn

(good for spontaneity)

'3 ^s1 React ^: * 393.9: 5 - (+ ^ 58.952) - - 65.022

cal / mol-eqn χ degrees

: 1,400 degrees χ (-65.022) = - 91.031 Kcal / mol-eqn : = - 91.0 ^ 1 Kcal / mol-eqn

J ^ g - hn - T ^ s - - 161.4 - (-91.031) = - 70.369 ^ G: - 70.369 Kcal / mol-eqn

(good for spontaneity) Heat generated by exothermic reaction Assuming a 2-minute cycle

- 70.369 Kcal / mol-eqn 70.369 x 9 (mol) χ 30 (cycles) = 18,999.63 Kcal / hour ·

? 75,390,531 BTU / hr
Note:
Assuming a 1-minute cycle

; 150,781.06 BTU / hr
Thermal energy required for dissociation

- 63,055.84 BTU / hr
Energy equality
2 minute cycle

75,390.531 - 63-055.84 = 12,334.691; btü) (excess)

The aforementioned reaction is exothermic, but results in

609819/0968

Sf .Jl

25493V0

a decrease in entropy or an impressively greater order in the system. The ^ H energy expression is favorable to a spontaneous transformation (/) H is negative), whereas the T j \> S energy expression is unfavorable (T ^ S is negative), ie the entropy S of the system increases during the transition from the initial to the final state. As the calculation shows, the reaction is capable of taking place spontaneously under the specified conditions, since the favorable J ^ H expression outweighs the unfavorable T ^ S energy expression.

Therefore, it is to be estimated that in accordance with the previously discussed thermodynamic principles, the process of the invention involves the production of hydrogen from water using iron or manganese as preferred reactants (catalysts) and also the conversion of the reactant to its original state in a novel manner performs. Since the hydrogen-generating phase of the overall process is exothermic, a good part of the heat generated by this reaction is used in the phase of regeneration of the reagent. It is noted, however, that additional heat may be required in the reactant regeneration phase and this heat is supplied by means of timed, controlled, prescribed internal electrical heating of the oxide in order to raise the temperature to the point of h H _di , from which the oxides dissociate or disproportionate the gaseous oxygen atoms from the pure metal atoms, the oxygen atoms being diverted into the outer atmosphere or directed elsewhere ₍ where they cannot recombine with the metal.

609819 / 0SB8

So &

During the period of time during which the heat dissociation process is taking place, for example, the oxygen will be removed from the reaction cartridges by introducing a calculated amount of hydrogen gas into the chambers in which the dissociation process is taking place. Alternatively, steam can be used to "purge" the oxygen from the chambers; any other obvious means for this purpose is applicable. The use of hydrogen or steam creates a train which removes the paramagnetic oxygen atoms and at the same time creates an atmosphere in the cavity or reaction chamber which is favorable to the inventive concept. According to the present invention, therefore, an unlimited number of cycles of hydrogen generation-reactant regeneration can theoretically be carried out without introducing impurities and without reducing the effectiveness of the reactant metal as a result of other undesirable reactions.

According to another aspect of the invention is an apparatus provided for carrying out the method according to the invention. This device is designed to work in this way and to function to create the essential environmental conditions prescribed, including carefully controlled heat, atmosphere, and monitoring and timing punctures. The device according to the invention is described with reference to certain preferred embodiments, which are presented by way of example and not in a limiting manner. The embodiments of the invention discussed in more detail Device are firstly a device for de-

609819/0968

i?

need in a motor vehicle, secondly a small power plant for use in an apartment and thirdly an economical one Unit. It is to be expressly noted that each of these embodiments can be appropriately changed to include in one to be usable in another environment.

The invention will be better understood and objects other than those already mentioned, upon review of the detailed description of the invention that follows. This description also makes reference to the drawing, in which the drawing shows
Fig. 1 shows an enthalpy diagram for the reaction of iron with steam

with formation of hydrogen and iron oxide,

2 shows a perspective view in an exploded arrangement of a device for generating hydrogen, partly with openings,
Fig. J> a schematic representation of the hydrogen flow through

the device according to Figure 1,
4 shows a schematic representation of the steam washer system of

Device according to Figure 2,
5 shows a horizontal cross section through a device for

Generation of hydrogen, partly with cracks, FIG. 6 a perspective illustration in an exploded arrangement of the electrical system of the device according to Pig. 5.
7 shows a perspective illustration in an exploded arrangement of a third device for generating hydrogen, partly with openings,

- Go 609819/0968

Pig. 8 a perspective view of the device according to FIG. 7,

Pig · 9 is a schematic representation of the process sequence in FIG Device according to Figure 7 in a first mode of operation,

FIG. 10 is a schematic representation of the process sequence in FIG Device according to Pig. 7 in a second mode of operation,

FIG. 11 is a schematic representation of the process sequence in FIG Device according to Fig. 7 with a different line type,

FIG. 12 shows a plan view of a partial valve of the device according to FIG 7, with hidden parts being shown with dashed lines,

13 is a front view of the partial valve according to FIG hidden parts are shown with dashed lines,

Fig.i4 is a front view of a rotatable valve element according to Pig.12,

Pig.15 is a plan view of the rotatable valve element according to FIG Fig. 14,

Pig.i6 a side view of a control valve of the device according to Figure 7, partially in section,

Fig.17 is a front view of the control valve according to Fig.16, wherein hidden parts are shown with dashed lines.

Pig.i8 a horizontal section of the control valve according to; line 18-18 in Fig. 17 and

19 shows a horizontal section of the control valve according to the line 19-19 in Fig. 16.

Example 1

The thermal efficiency (degree of efficiency) of a motor vehicle engine can be easily calculated. Usually data

609819/0968

Obtained through physical testing of a motor vehicle, because the real, the actual conditions correspond Efficiencies are usually much lower than the calculated theoretical efficiency, maybe only half. The practical ones Losses include errors in the complete combustion of the fuel and the exact duplication of the cycle process, the heat given off by the machine, friction, losses, etc. For the present case, however, it is both valid as well as meaningful, the thermal efficiency of a motor vehicle engine, which in a conventional manner with Gasoline powered, and then calculate this data with the calculated thermal efficiencies of the exact same Compare motor vehicle machines that run on hydrogen. It is then shown that the device according to the invention can be designed in accordance with the calculations in accordance with the theoretical requirements, and then to the The capacities needed to correct the losses could be added to design requirements, which occur in conventional machines, whether they work with gasoline or hydrogen.

The theoretical efficiency is the efficiency of the cycle and is equivalent to the amount of energy supplied, the actual one Work is implemented. The braking efficiency of a machine is the proportion of the energy supplied by the fuel, which is available as braking power in PS. In order to be able to determine the value of the energy supplied, the calorific value of the fuel must be known. This is in usual units,

6098 1 9/0968

expressed as British Thermal Units (BTU).

The number of BTUs released by burning 453 * 59 g of fuel is called the calorific value Qi. For high quality gasoline, this fourth is nominally 20,000 BTU each
453.59 g «The work of the machine can also be expressed in BTU
express because one BTU is equal to 778 χ Ο.3θ48 m χ 453.59 g of work. A PS that is produced continuously for one hour is therefore equivalent to 2546.4 BTU.

Since the specific brake fuel consumption is the same as that in 453.59 g of measured amount of fuel is used in one hour is burned to provide 1 horsepower, the thermal braking efficiency can be expressed as

2,546.4

BTU -

b.s.f.c. χ Q,

The amount of oxygen needed to keep fuel burning is easy to calculate,
when the basic chemical components are known. Usually it is assumed that gasoline is a mixture of many hydrocarbons that have approximately the same octane number as CgH ₁ O on average. If one assumes that the equation of connection between gasoline and air can be written as

C ₈ H ₁₈ + 12.5 O ₂ ■ + 47.5 N ₂ ■ y8 CO ₂ + 9H ₂ O + 47.5 N ₃

at 453.59 g (= LB) of fuel, the equation is:

1 LB.C ₈ H ₁₈ + 3.51 LB.O ₂ + 11.66 LB-N ₂ >

3 * 09 LB.CO ₂ + 1.42 LB.H ₂ O + 11.66 LBN ₂

609819/0968

7 549 3

1 LB-C ₃ H ₁₈ + 15.17 IBS. Air>

16.17 LB (products of combustion) (LB-pou-nd = 453.59 g) These equations represent the relationships with complete combustion. The incompleteness of the combustion chamber, incomplete Mixture of fuel and air, insufficient time for the reaction to complete, and other unfavorable factors prevent complete or perfect combustion.

Experience has shown that a slightly lean mixture of around 16: 1 is more economical than the aforementioned 15.17: 1 ratio. the excess air contributes to complete combustion; however, actually less work is being developed because of the Lean mixture contains a smaller proportion of fuel. Further leaning is uneconomical because of the degree of combustion the loading or loading is reduced. A slightly richer mixture, e.g. 12: 1, gives a little more power than the theoretical chemical burn ratio of 15.17: 1 · This is so because the extra fuel is more chemical Introduces energy into the combustion chamber and, although the combustion is less complete, the net energy release grows.

Motor vehicle machine (200 HP) gasoline consumption in BTU (full power)

Assuming a gasoline quality of 21,000 BTU per 453.59 6, and, since gasoline weighs 6.152 χ 453.59 g per 3.7053 l, then is 6.152 χ 21,000 - 129,192 BTU per 3.7853 L; and 21,000 BTU = Q.

609819/0968

the power delivered, calculated as 1 HP delivered during the 1st Hour, is 2,546.4 BTU and

2 r46 the thermal braking efficiency: BTE =

Since 1 HP - 2,546.4 BTU for 1 hour, 200 HP = 509 · 280 BTU for 1 hour - 141.47 BTU per second

Hydrogen required to replace gasoline: Since 1 χ 0.02832m ^ H ₂ (low net weight, 60 ° P, 1 atm) = 269 BTU and since a 200 HP motor vehicle engine needs 141.47 BTU per second for full power, the following applies:

_{= Oi52} 59 χ 0.02832 «Au per second.

269 BTU 0.02832 Tf?

Since 1 χ 0.02832 nAi ₂ for the combustion 2.38 χ 0.02832 nP air

required, applies to the fuel-air mixture H ₂ = 29.58 percent
Air = 70.42 percent

100.00

It follows that the total volume of fuel-air mixture that is consumed per second in the machine is 1.7769 x 0.02832 nr , of which only 0.5259 χ 0.02832 nr is hydrogen that has to be generated.

Steam throughput to generate the required Hg 0.5259 χ 0.02832 m Hp are required per second 648.0 g steam generate 72.72 gH ₂ = 8.911 g steam per gram H ₂

H ₂ . = 0.00531 ⁼ 2.408563 g / 0.02832 m ⁵

609819/0968

Then: 0.5259 (0.02832 ur ⁵ ) x 2.408563 - 1.26667 gH ₂

and 1.26667 χ 8.911 * = 11.2875 grams of steam per second = 0.02488 χ 453.59 g steam per second

Assuming full power at 120 mph, the motor vehicle would be about 12 miles per 3 * 7,853 liters of water

drive at this speed.

Taking these explanations into account, Fig. 2 is now considered, where the major components of an inventive device 10 are shown, which can be used in a motor vehicle is.

The device 10 comprises a ceramic cylinder casting 12, the Poured in a manner known per se from a slurry or a slurry of suitable ceramic material and placed in an oven is burned. Suitable materials for the ceramic cylinder casting are mullite or, preferably, alumina AlpO-. According to In the drawing, the cylinder casting 12 has seven cylinders which are numbered 1 to 7 for the sake of simplicity. In No. 1 to 3 and No. 5 to 7 cylinders are used with reactant tubes 14 made of a suitable material that is inert to the reactions and resistant to the temperatures that occur in the device. A suitable one Material is e.g. stainless steel. The reactant tubes are in the form of books, if necessary are interchangeable. The walls of the cylinders of the cylinder casting 12 are from about 0.318 cm to 0.635 cm thick. The ceramic Material has the following significant physical properties

609819/0968

fr

shafts: high electrical insulation properties, extremely high war · «· permeability, chemical compatibility with the system, easy manufacturability and hard surfaces. In the cylinder No. 4, a heating element 16 is used, the purpose of which will be given below is explained. As already explained above, the reactant can be in various physical forms, the main requirement being that of maximum surface area of the reactant is exposed to the steam to create a large reactant surface area to accomplish. Therefore, the reactant is processed to form such a large surface area. This is done in that the metal is crushed into particles which comprise fine powder or lumps of relatively large size; i.e. the large size of the irregular chips is in a range of about 0.65 cm to 1.27 cm. Another shape of the reactant is a continuous tape, thread or wire and the latter is used in the present embodiment. A bundle of reactant filaments 18 is in each reactant tube 14 packed.

A steam collector 20 is provided to, if desired, with the Device to be able to generate and deliver hydrogen immediately and quickly. The steam collector 20 receives water from a reservoir 46 via a feed line 22 and a return line 24, the two lines circulation between the steam collector and Ensure storage container. This is especially important in cold weather when the water in the reservoir tends to to freeze, and this is prevented by the constant circulation to the steam collector, where the water is heated. Of the

6098 19/0968

61 -for

25Α937Ο

Water storage tank is what a normal motor vehicle the fuel tank is on. From the steam collector 20 there is steam guided via a steam line 26 to the hydrogen generator. A conventional thermoelectric generator 28 is provided to to supply the requirements of the device in terms of nominal electrical power, with the usual electrical system of the motor vehicle for this purpose is usable.

The hydrogen generated in the cylinders flows through a hydrogen manifold 30, a hydrogen pump 32 and a hydrogen line J54 to an engine hydrogen supply device 36. A hydrogen reserve tank 38 is also provided. A control valve 4o is provided to sequentially feed steam into cylinders Nos. 1 to 3 or 5 to 7 depending on their operation, to feed hydrogen from these cylinders in the hydrogen generation circuit to and around the manifold Oxygen-containing outflow of the reactants to conduct regenerating cylinders. In the embodiment shown , the control valve 40 is a rotary valve operated by a valve actuation motor 42. All these parts of the device, which are operated at a high temperature or are to be kept at a constant elevated temperature, are housed in a body 44 made of ceramic foam. The Keraraikehaum forming the body 44 is described in US Pat. No. 3,762,935.

In operation, the device must first run through before the cylinders reach a temperature that is high enough

609819/0968

to get the response. For start-up, electrical energy is supplied to heating devices in the steam collector and at the same time to the reactant in the reactant tubes (reaction chambers), which is determined and directed by means of the control valve 40. As stated above, the reactant metal of the reactant strands becomes a resistance heating device due to the electrical current supplied. The mass of the tightly packed metal wires, because they are partially oxidized, is quickly heated to red heat. The voltage and current required for all of this can easily be determined by a person skilled in the art. Steam is generated in the steam collector 20 and is conducted through the steam line 26 into the inlet end of the No. 4 cylinder, where it is further heated by the heating element 16. The superheated steam leaves cylinder no. 4 and is directed by means of control valve 40 into either cylinder no. J> or cylinder no. 5, depending on which group of cylinders is intended for hydrogen generation by control valve 40. It is assumed that cylinders # 1 to J5 are intended for hydrogen generation, so that the steam is fed into cylinder # 5 by means of the control valve 40. As noted, the reagent filaments 18 of cylinder # 5 are preheated to red heat. When the steam reaches and passes through cylinder # 3, the reaction between the steam and the reactant becomes exothermic. Hydrogen gas is separated from the steam and passes through cylinders # 2 and # 1.

The automatic programmed control system, not shown now switches: the electrical energy from cylinder no.3

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254937Π

and closes a circuit through which electrical energy flows to cylinder no. 2 to preheat its catalyst or reactant filaments 18 to exothermic takeover conditions, after which the control system opens the circuit to cylinder no. and the circuit to cylinder no. 1 closes. If all three cylinders are exothermic, there is no need to continue adding electrical energy to them. 3 shows the flow of steam and hydrogen through the device by means of arrows. The flow goes through cylinder # k- where the steam is preheated and then through cylinder # 3.2. and 1, from where it passes through the hydrogen distributor and the hydrogen pump 32 via the line 3 ^ to the hydrogen reserve tank 38 and to the machine hydrogen supply device 36.

If it is determined by a monitoring device that the predetermined proportion of reactant in the cylinders No. 1 to 3 is converted into Oxydium, then the control device continues cylinders # 5 to # 7 operate in the same way. When the exothermic temperatures are reached in the cylinders the electrical power supply to these cylinders is cut off and the circuits of the cylinders are closed No. 1 to 3 switched on in order to raise their temperatures to the value required for the dissociation of the metallic oxides. When the metal oxides dissociate, either steam or hydrogen in small amounts passes through the appropriate cylinders to accelerate the reaction process and to pump the oxygen out of its cylinders.

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'■ ra- 254937'n

So when the device is working and alternating between hydrogen generation and reactant regeneration, then three cylinders always generate hydrogen and three cylinders are always regenerated for the next generation process. When the apparatus operates continuously in this cyclic manner, the whole ceramic Zylindergußstück reaches a _r equilibrium temperature of about 1,900 ⁰ F to 2,000 ° P. The electrical device that senses this temperature level automatically stops the provision of electrical energy, unless during the required increase to the dissociation level during the reactant regeneration, as far as this increase is necessary.

The overall system is with reference to Fig.2 and the hydrogen system is described with reference to Fig.3. For a full understanding of the operation of the device various other sub-devices and sub-systems would also need to be described. E.g. is the fuel supply device an essential part of the overall device. The fuel supply device uses a reservoir 46 or tank, which is the petrol tank of a motor vehicle is equivalent to. In fact, that's what you see currently in automobiles Use the used gasoline tank as a water reserve tank by adding only a single pipe and the existing one Fuel supply line that connects the fuel tank and connects the carburetor, on the one hand to the steam collector and on the other hand to the engine inlet of the manifold will.

6098 19/0968

J 254937Γ)

As already indicated, a feed line 22 connects the fuel tank and the steam collector 20, and a return line 24 is provided between the steam collector 20 and the fuel tank. These create two significant conditions. First, a constant and adequate flow of water to the steam collector 20 is established. This is important because of various stress demands placed on the motor vehicle driver. The return line is according to Fig.4 connected to an inner overflow standpipe 44 which regulates the water level in the steam collector 20. Second, the leads Return line 24 excess water back to the main reservoir 46 and acts as a heat exchange unit by returning heated water to the reservoir. The reservoir 46 thus acts like a large, considerable heat-collecting heat drain, which removes any possible excess heat from the main unit removed, which is distributed in the water reservoir. As a result, the temperature in the storage container to about 50 to 65 C is kept there will be any possibility of freezing during of the operation avoided. A small amount of alcohol in the reservoir 46 prevents severe overnight freezing in cold weather. The alcohol does not interfere with the reaction in the device.

The steam collector 20 is to be regarded as a tank with very hot water, which provides steam provided by boiling water. If there is an excess of generated steam, the pressure increases and steam condenses in water of the steam collector and heats this water. When the pressure drops, the water boils and leads to the lack of steam again. This is a very simple one to yourself

609819/0968

regulating principle.

Four electrical heating elements 48 are provided in the steam collector 20, that give off enough heat to create working steam in 10 to 15 seconds. The automatic control device operates the heating elements individually or collectively for intermittent periods of time to the desired temperatures to maintain. If the entire device has been in operation long enough that the exothermic reaction of hydrogen generation runs and the entire mass of the unit, which is packed in the ceramic foam housing body 44, has heated up, then the Heating elements 48 switched off automatically. According to Fig. 4 steam flows from the steam collector 20 via the steam line 26 and is blown into the No. 4 cylinder through a suitable nozzle. The reaction cylinder and the associated components are shown in Fig.4 a part 52 indicated. A return line 54 is provided to return excess steam to the steam collector. As will be made clear further below, excess hydrogen can also be used and return oxygen via return line 54, wherein they are catalytically converted back to water which is added to the steam collector 20.

It is calculated above that a motor vehicle with a rated power of 200 HP a throughput of I8.88j5 enr (0.66678 cubic foot) steam of 1 atm pressure per second is required for the full Power of the machine to obtain the necessary hydrogen. Since these are the numbers that theoretically apply to the selected machine size calculated, the overall device should be able to add additional

6ü98 19/0968

borrowed at least 100 % more to cover the natural losses associated with ineffective automotive energy. The apparatus should also have facilities for generating additional capacity to meet incidental energy consumption through equipment such as air conditioning and other accessories. The volume capacity of the device is given in 0.02832 nr by the equation V-IfR ² x L, where V is the volume in 0.02832 nr ⁵ , "(\ = 3.1 ² Ho, R the radius of the cylinder, L the The length of the cylinder and D is the diameter of the cylinder. Assuming that three cylinders are currently working for hydrogen production and that the cylinders are 10.16 cm in diameter and 91> 44 cm long, then the volume is 22,231 * This calculation shows that each working unit formed by three cylinders together has enough volume capacity that the requirements with regard to steam throughput can easily be met, that steam is blown in in such an amount that the working unit is filled and emptied one to three times per second The steam speed does not become a problem with this consumption because it is in the range of 2.7 ^ 52 m to 8.2296 m. The device is designed so that the steam pressure cannot rise to more than 68,038.5 g per 6.452 cm This increases the steam f yield of the system from 1 to 10 atm. The volume flow of the steam is proportionally reduced because the weight of the steam at 10 atm is 136 to 2,751 * 5 g per 0.02832 nr, whereas the steam at 1 atm is 16.912 g per 0.02832 v? weighs.

With regard to the reactant, it is important that the transverse

6U98 1 9/0968

- ff 25A937Ö

The cross-sectional area of the continuous reactant filament is so large that a malfunction in the cycle timing, which would result in the reactant being exposed to hydrogen generation for a greatly extended period of time, does not convert the reactant into the oxide over its entire cross-sectional area. In general, it is desirable that the oxidation process be limited to the outer 80 % of the reactant, since if the conversion occurs to a large extent, the reactant is physically weakened and its continuity can be interrupted by severe vibrations.

The controller is programmed to take advantage of another interesting location. It has been found that the oxidation number of the metal oxide, be it iron or manganese or an alloy of these two, precisely related to the measured ohms resistance can be set. An increase in the oxidation number increases the ohms resistance is seen quite considerably, and this phenomenon is repeatable. Since oxidation involves a loss of electrons, this phenomenon is predictable.

It is also known that the temperature can see the electrical ohms Resistance affects, although this effect is nowhere near as predictable as the oxidative effect. In any case it is known that the higher the oxidation number, the higher the ohmic resistance for the current in the heating circuit. Therefore, the portion converted into oxide can be

6098 19/0968

Determine reaction center precisely by monitoring the resistance at timed test intervals. The integrity of the unit is then protected in terms of strength and electrical conductivity by never allowing the oxidation process to convert more than 80% of the cross-sectional volume of the metal. The remaining 20 % is in the core of the metal along the length of the metal. This ensures sufficient physical strength and electrical conductivity.

However, as additional protection, a separate and independent resistance heating element can be provided in the bulk of the reaction material. This will be described in more detail in connection with another embodiment of the device. As should also be noted, the exothermic reaction of hydrogen generation causes temperatures of 1800 to 2000 ^° F which are present throughout the reaction time. The ceramic insulation compound of the unit effectively preserves and shields this temperature. Thus, if a group of cylinders is switched from hydrogen generation to reactant reconstitution, the temperature will remain at 1800 to 2000 F and only needs to be raised an additional 200 to 500 ° F. The energy required for this small increase in temperature is insignificant and can be supplied by means of the electrical device of the motor vehicle.

Example II

The second example shown in the drawing, Fig. 5 *

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254937h

direction 56 is a unit called the "residential power plant"
can be. This device has two reaction chambers 58, 60 which are formed by a pair of concentrically arranged reaction tubes 62, 64 which are held by end closure devices 66, 68. Each of the reaction chambers 58,
60 is filled with a reactant 18 in a suitable form as previously described.

Water passes through a feed line 22 into a steam collector 20. A water return line 24 allows the water to circulate through a water storage container (not shown). As with the steam header of the first embodiment, heating elements 48 are provided to maintain the required temperature in the steam header. From the steam collector 20, steam passes through a steam line 26 and a control valve 40 to one of the two reaction chambers 58, 60. 5, the control valve 40 is directing steam to the outer reaction chamber 58. When the steam flows over the heated reactant 18, hydrogen is generated and the reactant is converted to an oxide. The hydrogen leaves the device through an outlet 70. While the outer
Reaction chamber 58 is in the hydrogen generation phase, the inner chamber 60 is in the reactant regeneration phase. To purify the inner reaction chamber 60 of oxygen as it is released, a measured amount of hydrogen is diverted through exchange ports 72; this mixture of oxygen and hydrogen is vented through an outlet 74 in the end cap 68.

6U9819 / 0968

Pig.6 shows the electrical equipment of the entire device schematically. The operation of the overall device is regulated by a digital control device 76 and an intermediate device 78. This control device regulates heating elements 48 of a steam collector 20, a vent exercise motor 42, heating elements 80, 82, 84 and 86 and a thermoelectric generator. The reactant 18 is not heated by passing electricity through it, but is arranged around the heating elements 80, 82, 84 and 86, which provide the necessary additional heat for start-up and for the reactant regeneration phase. The outer and the inner
Reaction tubes 62, 64 are made of ceramic and lined with a suitable material, for example stainless steel, and there is a considerable heat exchange between the two reaction chambers 58, 60 via the wall of the inner reaction tube 64. In this way, the exothermic reaction of the hydrogen generation phase supplies heat to one reaction chamber in order to keep the other reaction chamber at a high temperature, so that only a small amount of energy has to be supplied to the
Raise the temperature to a slightly higher value for the purpose of dissociation or disproportionation of the metal oxide.

Example III

In this third preferred embodiment, which is shown in FIG
to 11 is shown in the drawing, manganese is used as a catalyst or reactant. As already mentioned,
the element manganese forms a multitude of oxides including

6Ü9819 / 0968 ^κ

■ τ *

- * & - jtf? R 4 9 3 7 Π

Lich MnO, Mn ₃ O ^, Mn O ^ and MnO ₃ . Oxides of the formula Mn ^ O ₂ can also be specified as MnO.Mn 0, and contain 1/5 of the metals in the +2 oxidation state and 2/3 in the +3 oxidation state. The structure of these oxides consists of an ionic lattice in which Mn ions, Mn ions and O ~ ions alternate in various regular patterns. At ordinary temperature and pressure, all of the oxides listed are thermodynamically stable with respect to decomposition into metal and oxygen gas. Oxides of manganese, which are in different oxidation states, have different relative stabilities and thus have the ability to partially dissociate or disproportionate. However, such reactions do not take place to any detectable extent at ordinary temperatures. For example, MnOp dissociates normally at 535 ° C. and Mn ₂ O, normally at 1080 ° C. It can be seen that an increase in temperature and / or pressure increases the dissociation process in an approximately linear manner. The manganese can be said to act as a reductant, removing the oxygen from the steam, thereby separating the oxygen.

FIG. 7 shows the device 86, which comprises inner and outer reaction cylinders 88, 90 which, similar to FIGS. 5 and 6, are arranged concentrically to one another. The reactant 18 is in the form of chips of irregular shape and edge configuration and in the mass of manganese chips a heating element is embedded, which comprises a small ceramic tube 92 which carries a heating element 9k which is embedded in an inert material 9β which is electrically is not conductive.

6098 19/0968

-AT- ng ? 5 /; 9 3 7h

Such a material is e.g. silica. The reaction cylinders 88, 90 are secured by means of two plates 98, 100 and clamping rods 102 and secured by suitable means such as screws 104. A control valve I06 regulates the operation the device. The structure of the control valve I06 is described in detail below; the task of the control valve is to direct the steam flow into the device and the hydrogen and oxygen flows through the device and to lead out of this. A partial valve I08 is a convenient means of directing the output of the device either to where it is doing useful work or back to one to conduct not shown steam collector. The steam collector corresponds to that in the previously described embodiment and is not discussed further here. An overall control device 110 regulates the overall operation of the device. As in the previous embodiments is the control device of conventional design and has suitable means for measuring the various parameters such as temperature, pressure, and reactant composition and the like, as well as calculating the desired temperature and maintaining the operation of the device. The entire device is encased in ceramic foam material according to US Pat. No. 3,763,935, which forms a housing 112.

The method of operation of the device can be understood from FIG. Water passes through a feed line 22 into a steam collector 22, a return line 2k being provided which serves the same purpose as in the previous embodiments. Over a

6098 1 9/0 9 b 8

Steam line 26, steam flows to the control valve 106. Without here to go into the structure of the control valve 106 in detail, it is noted that there are essentially four sections A, B, C and D. In Fig. 9 the control valve is in the position shown that when hydrogen is generated in the reaction chamber 114, which is delimited by the inner reaction tube 90, and occupies upon regeneration of the reactant in the outer reaction chamber, through the annular space between the inner Tube 90 and the outer tube 88 is formed. The steam passes through the steam line 26 to section C of the control valve 106 and can pass through a line 118 to a steam manifold 120 and then into the reaction chamber 114. When the steam enters the reaction chamber 114 and contacts the hot reactant 18, hydrogen is generated, which in a Hydrogen manifold 118 arrives. From this tfer arrives through line 120 to section A of valve 106 and from this into a line 122. At a division T 124, a predetermined amount of the hydrogen is passed through a line 126 derived to section D of valve 106 and passed from section D of valve 106 into outer reaction chamber 116, where the regeneration of the reactant takes place.

Starting from the dividing T 104, the hydrogen flow goes through a line 128 to a section A of a partial valve 1; 50. The partial valve 1 ^ 0, which is described in detail below is shown in a position in which the hydrogen flows via a line 1 ^ 2 to the steam collector 20. Of the The reason for this becomes clear from the following description.

609819/0968

254937 (1

While hydrogen is generated in the reaction chamber 114, metal oxide is reduced back into metal in the outer reaction chamber 116, wherein the released hydrogen is washed out of the reaction chamber by means of the measured proportion of hydrogen that accesses via port D of control valve 1O6. The oxygen mixed with the small amount of hydrogen arrives through a line 134 to section B of the control valve 106 and then via a line I36 to section B of the partial valve 130. The partial valve I30 is shown in the position in which the mixture of oxygen and hydrogen is passed back into the steam collector 20 through a line 138. The hydrogen and the oxygen flowing through lines 132 and I38 in the Steam collector 20 arrive, touch the catalyst 14O, whereby they are converted into water. The reason for the return of the hydrogen and oxygen in the steam collector and for the catalyzed conversion back into water is easy to explain. It should be remembered that this device is used under economic union conditions, for which purpose it is used is to supply a manufacturing process with hydrogen or a mixture of hydrogen and oxygen, if desired, wherein the manufacturing process includes, for example, a kiln used for the manufacture of cement, masses or the like. In this case, the device must be continuously in operation in order to delay or delay due to a start-up avoid. There is therefore a cycle between hydrogen generation and reactant regeneration in the reaction chambers 114 and 116 put into operation, in which the hydrogen produced by oxygen can be fed back into the steam collector, where it is ■

609819/0968

-en- Zl 254937Ü

catalytically converted back into water. If hydrogen If hydrogen and oxygen are required as fuel, the partial valve 1 ^ 0 is moved to its second position, in which hydrogen flows out through line 142 and a mixture of hydrogen and oxygen through line 144. 10, the device 86 is shown with the valve 106 in its second position, with the outer Reaction chamber 1o6 hydrogen is generated while the reactant in the inner reaction chamber 114 is regenerated will. Steam flows from steam collector 20 through steam line 26 to what is shown schematically as the upper region of section C of control valve 106. The steam comes from here through line 146 to reaction chamber 116 where hydrogen is generated and through line 1J54 to section B of the control valve 1O6 reached. From the section B of the control valve 106 is a measured proportion of the hydrogen at a Dividing T 148 branched off to section D of the control valve 106 and fed from there to the inner reaction chamber 114 in order to remove oxygen therefrom, as far as this is released from the reactant. The rest of the hydrogen flows off the line 126 into the line 128 and from there into section A of the partial valve 1JQ. The oxygen and hydrogen that come out get out of the inner reaction chamber 114, flow through the line 1jj6 to section B of the partial valve 1 ^ 0. In two Lines 154, 156 are provided flow control valves 150, 152, to control the flow of hydrogen to the reaction chamber which is currently in use for reactant regeneration. The start-up of the device 86 is not discussed; the expert

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2S49370

recognizes, however, that the approach is the same as with the two previous embodiments is performed.

Various advantages of this embodiment can be seen. That Partial valve 1 ^ 0 can be set manually or independently so that that the hydrogen or the hydrogen-oxygen mixture is whole or partially diverted through lines 142 and 144. When the embodiment is used in an automobile, throttling can be achieved by regulating the partial valve 1 ^ 0 and can also be a stoichiometric mixture of hydrogen and oxygen of the motor vehicle engine for combustion are supplied, so that no outside air is required for the combustion, which is usually nitrogen-containing. The possibility, that the machine emits nitrogen oxides is minimized or eliminated. Although this embodiment is described above in terms of on the supply of a fuel mixture to an economical manufacturing process, can also be one of heating A furnace used for a building or a fireplace insert that generates electricity for an apartment or another building will. Furthermore, hydrogen can be withdrawn from line 142 which then reacts with nitrogen for the cheaper and more efficient production of ammonia, the ammonia for some the known purposes, e.g. the production of artificial fertilizer, can be used.

Although the regeneration of the reactants is referred to on the disproportionation of the metal oxide and the removal of the evolved oxygen by means of a little hydrogen from the

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Reaction chamber, what happens is more complex. The hydrogen entering the reaction chamber, in which the regeneration of the reactant takes place, actually reduces some of the metal oxide to metal by removing the oxygen and moving it out of the reaction chamber, while at the same time disproportionation takes place and that released in this reaction Oxygen is removed from the reaction chamber. Mn _{p is} 0, disproportionated at temperatures above I.080 ⁰ C or 1,976 P and the hydrogen generation reaction takes place at 1,077 ° C or 1,970 ° P. The steam entering the reaction chamber, in which the hydrogen generation takes place, is at a temperature of 36I ⁰ P and this low temperature keeps the Mn ₂ CU in the reaction chamber at a temperature just below the disproportionation level. However, no steam gets into the reaction chamber in which the reactant regeneration takes place, and the reaction temperatures created by the hydrogen generation in the other reaction chamber, the temperature in the reaction chamber of the reactant regeneration phase to the disproportionation level . The ceramic structure of the ^p . Reaction tubes can exchange heat freely between the reaction chambers. The weight of the reactant, the weight of the product obtained and the working temperature are now considered.

⁶ \ s) ^{+ 11 H2} ° (S> 5M _n 0 _{2 (s) +} M _n 0 _{(s) +} 11 H ₂

Λ H ⁷⁰⁰ °; 0 11 (-65.9) 5 ((-126.4) -92.6 form

609819/0968

254937Π

S ⁷⁰⁰ ·: β (+ 8.2) 11 (+51.2) 5 (+15.9) + 17.2 1 x \ ^H React ^: "72 ^, 6 - (-625.9) = - 98 , 7 kilo cal / mol-eqn

,: + 508.54 - (612.4) - - 103.9 cal / mol-eqn χ degrees - 700 degrees χ (-103.9) = - 72.73 Kcal / mol-eqn = I & - T ^ S

- - 98.7 - (-72.73) "= - 25.97 Kcal / mol-eqn (exothermic)

- - 25.97 Kcal / mol-eqn

Molecular and formula weight:

Formula: 6Mn + 11H _P O> 5MrIO ₉ + MnO + 11H _P

6 (54.9t) 11 (18.02) 5 (86.93) (70.93) 11 (2.016)

Y / J / IJ / ^J '

Grams: 329.64 198.22 434.65 70.93 22.176

Required net scrap per hour at full capacity. Minimum BTU

j-net) 1,250,000 BTU / hour

It has been found that self-reduction or disproportionation does not drive out all of the oxygen associated with the manganese, but only 45.4545 % of it. The remaining oxygen must be removed by returning a percentage ($ 54.5455) of the hydrogen produced to the reaction chambers which are currently operating in the reduction phase. This moving stream of hydrogen removes the secreted oxygen and brings it back into the vapor collector as described above. Since the minimum net demand is 1,250,000 BTU per hour, it must be assumed that this net demand of 1,250,000 BTU is 45.4545 % of the total volume that the unit produces, making 54.5455 % of the hydrogen output.

■ ■

booty can be used internally as a reducing agent ^ gas flow.

603819/0968

JL 36 2 549 3 711

Therefore the total required yield is:

1,250,000 = 2,750,002.75 BTU per hour

0.45, 4545

A conversion of the total output in grams shows that water gas is 3ΟΟ-318 BTU per 0.02832 nr ⁵ :

2,750,002.75 BTU / hour = 9,166.68 χ 0.02832 it? per hour 300 BTU / 0.02832 nP

Since hydrogen gas EU 2.4iqpro weighs 0.02832 nP , 9,166.68 χ 0.02832 before per hour can be converted into grams by multiplying: 9,166.68 χ 2.41 = 22,091.69 grams per hour

There are several variables that can be added to the volume to control the overall yield, e.g. by multiplying the original formula by a larger multiple or by the cycle is accelerated to shorter periods of time or by increasing the vapor pressure by adding the reactant manganese a larger amount of water is offered in a shorter period of time. When a combination of these practices is used If the multiplier 32 is chosen arbitrarily, the reactant masses can be determined as follows:

6Mn + 11H ₂ O -> 5MnO ₂ + MnO + 11H ₂

³² w i] / II ■ J / ..

Grams $ 10,548.5 6,343.1 13,908.8 2,269.8 709.7

453.59g 23.26 13.98 30.66 5.0.2 1.564

Since the unit generates in one of the two reaction chambers, the length of a passage or cycle can be determined:

--Ό9 "' 6098 19/0 968

254937 (1

22.091.69 (Gramni / hour) - 31.1282 cycle / hour

709.7 (grams / cycle)

The number of cycles can be accelerated, which results in the following:

₌ ^ ^ _{Grams / cycles} 45.0 (cycles / hour) '

And if it is accelerated even more:

= 368.1 ₉ 48 grams / cycles 60.0 (cycles / hour)

It is shown that 31.1282 cycles per hour, each lasting about 2 minutes, produces the total yield of 22,091.69 grams per hour. It follows that, as shown, the cycle time can be accelerated, but the steam input is increased by increasing the steam pressure (and density) proportionally, thereby increasing the total and net yields of hydrogen Hp.
For example: 45 cycles / hour χ 709.7 (grams H ₂ / cycles)

= 31,936.5 grams / hour or: 60 cycles / hour χ 709.7 (grams Hp / cycle)

= 42,582.0 (grams / hour)

In order to do this, it is only essential that the supply of vapor molecules be increased in direct proportion to the decrease in the reaction time.

This procedure for increasing the yield of course has a limit set by the reaction rates and temperatures. The actual consumption of water is only a maximum of 45.454 to 5% of the water is converted into steam _y EDAS. Physically, 54.5455 % of the volume and weight of the water continuously circulate back by putting the water in

609819/0968 - * £

88 - * - 254937t)

Steam, this in hydrogen and oxygen and this back in Steam can be converted.

If the unit is a closed system with regard to this amount of water, then the total consumption of water only corresponds the amount necessary to produce the net 1,250,000 BTU, which are originally desired and which are provided by the partial valve 130 are withdrawn, and are fed to an incineration or other use.

The total conversion of 6,343 * 1 gram of water results in 7.1O9 * 7 grams of hydrogen according to the calculation above. When the unit is running at maximum output, the water consumption is 45.4545 % of the amount that is constantly converted into steam. Hence, D, 454545 6,343.1 grams / cycle converted = 2,883.2244 grams. If the unit is operated at a 30 % reduced rate, 6,343 1 gram / cycle converted χ 0.454545 = 2,883.2244 grams: then : 0.30 χ 2.8832244 864.9673 grams of H ₂ are consumed.

The construction of the partial valve is such that a withdrawal of hydrogen at the same time withdraws the amount of oxygen corresponding to the equilibrium. This makes oxygen, if desired intended for the combustion of hydrogen and will be the remaining one water and oxygen passed into the steam collector where the catalyst grid converts the hydrogen and oxygen in the steam for another cycle. This re-creation of water and the heat development associated with this reaction is minimized.

6098 19/0968

ren the energy required normally for a conversion of water in steam is required.

It has been shown that the wiikiliche consumption of water 2.88 ^, 2244 grams per cycle at 31 cycles per hour, where the vapor pressure is 155 x 455 * 59 g / 6.452 cm. The consumption is so:

2,883.2244 χ 31 = 89,379.9564 grams / hour

- 197.0491 x 453.59 grams / hour - = 23 _f 32 x 3.7853 lite ^ hour

Required preliminary energy
1. The means of reduction

a) The specific heat of Mn - 0.250

b) It is calculated that at least 10,548.5 grams of manganese are required for each of the two reaction chambers; the overall demand is then: 10,548.5 χ 2 - 21,097.0 grams in total.

c) It is necessary to keep the temperature of the manganese at about 500 ° C raise to allow a slight temperature drop, which occurs due to the cooling effect of the steam, which is approximately 183 C before the exothermic reaction begins, to sustain oneself.

d) Therefore: 21.097.0 χ 0.250 x 500 ° C - 2.637-125.0

= 2,637,125.0 cal - 2,637.13 kilo cal

Conversion to JSBUt

2,637.13 χ 3.96832 = 10,464.96 BTU

609819/0968

SO ~ 254937Π

2. The ceramic tubes

a) The specific heat of the AIpO ^ of the ceramic tubes at 500 C. = 0.245

b) A total of 10,206 grams of AIpO- ^ are to be heated to 500 C. the required heat is then:

0.245 x 10.206 χ 500 ° C - 1.250.235 cal

= 1,250.24 kilocal conversion to BTU:
1,250.24 χ 3.96832 - 4,961.33 BTU

The water

a) It takes 1,193.7 BTUs to convert 453.59 g of water to steam at 155.6 χ 453.59 g / 6.452 cm ² pressure and 361.4 ° F.

b) If 3,628.72 g of water are converted into steam for start-up, the heat required is:

8 x 1,193.7 ( > --9,549.6 BTU

4. Conversion of the preheating energy from BTU to kilowatt hours:
10,464.96 + 4,961.33 + 9,549.6 = 24,975.89 BTU and
24,975.89 BTU x 2,928 χ 10 ~ ^ kilowatt hours / BTU = 7.31 kilowatt hours

Thermodynamics of the continuous mode of operation

1. As stated above, the following applies: -ΔG = 25.97 Therefore, ^ S ₁ G = 25.97 Kilocal / mol-eqn

2. The moles to be considered here are the oxides of manganese Formula, namely MnOp and MnO and the formula requires a total of 6 moles for equilibrium.

609819/0968

3 · The multiplier was 32. Therefore:} 2 χ 6 = 192 mol 4. To calculate the free energy (/ JG) of the reaction for one cycle, multiply:
192.0 χ 25.97 (kcal) - 4986.24 Kcal / cycle "

5 To calculate- * Λ G for one hour, multiply:

x 31 ^ g ₅ = 154,577.44 Kcal / hour

Conversion to BTU:

154,573 * 44 χ 3.96832 - 613,396.87 BTU / hour

6. Heat loss due to radiation from the body of the unit The unit housing 112 has a surface area of 26,477.3265 cm and the insulation has a K-factor of 1.25.

If one assumes a working temperature of 430-450 C and an outside temperature of 85 ° P and an insulation thickness of 12.7 cm (two materials), then the heat flow through the insulation is nominally 125 BTU / hour. 929.029 cm ² .
125 x 26,477.3265 cm ² = 3,562.5 BTU / hour

7. In continuous operation for converting heat Energy (heat) required in steam per hour 433.28 χ 453.59 g of water must be used for continuous operation converted per hour. Since it takes 1,193.7 BTUs to evaporate 453.59 g of water into steam, the energy required per hour is: 1,193.7 x 433.38 = 517,325.71 BTU

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254937Π

8. Total energy balance for one hour

a) Entered energy BTU

1) total preheating - = 24,975 * 89

2) overall requirement to
43 ^, 38 χ 453 * 59 δ in steam

convert - 517,425.71

total entered energy 542,301.6

b) Submission of Js G in BTU 613,396.87

c) 613,396.87 - 542,301.6
(Submission) (input)

J ^ G (net) = 71,095.27 BTU / hour

The total heat required to produce steam at boiling point and at a given pressure is the sum of the latent heat of vaporization of the vapor and the heat generated by the same Temperature contained in the water from which the steam is formed. The total heat of the steam increases slowly. However, the latent heat decreases almost in proportion to this Increase in boiling point.

The space occupied by a given weight of steam decreases roughly proportional to the increase in pressure. In this regard, steam forms an ideal gas with no temperature change according to Boyle's law. These physical characteristics explain the spontaneous boiling of water, above which the air is sucked out will. This effect can be achieved with hot water for everyone Duplicate temperature and each pressure. E.g. the boiling point is of water under a pressure of 100 453.59 g 327.6 ° P

and the boiling point of water under a pressure of 155.6 χ

6U98 1 9/0968

254937η

453. »59 ε 361.4 ° ρ. If the pressure in a steam generator is reduced from 155.6 χ 453.59 g to 100 χ 453.59 g by venting steam, then the water boils spontaneously and absorbs its own heat by boiling until it reaches a temperature of 327.6 ° P, which is the boiling point of water at a pressure of 100 χ 453.59 g.

Due to this property of generating steam as a result of a reduction in pressure, steam collectors form a reservoir of steam, which can be withdrawn to sustain a temporary overload period. In other words, the steam collector generates steam faster than heat can usually generate, whereby the heat difference is supplied from the heat stored in the water itself will. It goes without saying that this reserve is limited and needs to be renewed in order to remain in force.

It is noted above that the regeneration of hydrogen and oxygen in vapor evolves the heat which is known to be associated with the regeneration reaction. In fact, the formation of steam evolves the same amount of heat that was required to generate the steam. Since steam is constantly circulated back through the unit in which the reaction of removal of hydrogen and regeneration of steam H ₂ O are in equilibrium and since 54.5455 % of the reacted steam is constantly regenerated as steam, the energy requirements for the conversion of Steam is used to generate such steam that is consumed by the 45.4545 # of product yield that can be diverted out of the cycle and converted into work.

609819/09 6 8

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2549 ^ 70

Fig. 11 shows a further possibility for distributing the product yield between the required Mifl & imum and the back-circulating 54.5455 % of hydrogen. As stated above, the manganese is reconstituted by heat alone up to a minimum of 45 * 4545 %. The remainder of oxygen is drawn off by the excess of hydrogen which is passed through the reaction chamber for this purpose.

The heat-reduced and the hydrogen-reduced oxygen leaves the reaction chamber in the specified proportions and enters, in a violently moving, mixed, but separated state, the partial valve 1 ^ 0, whereby 45 * 4545 % of this mixture of hydrogen and oxygen to the one leading to the outside Line 144 and 54.54? I> % of the mixed gas can be passed back to the steam collector to become steam again via line 1 ^ 8.

The ignition temperature of hydrogen in oxygen or air below atmospheric pressure is 58o-59O ° C or i.071-1.094 ° P. The ignition temperature of hydrogen is fairly precisely determined under a given set of conditions and is the one stated Range results from the fact that the hydrogen is not mixed well enough with the oxygen or the air. The point of inflammation of hydrogen decreases with increasing pressure. This compression increases the temperature, which of course brings the gas closer to the ignition temperature.

In the embodiment according to Pig. 11 an automatic release

6 U 9 8 1 9/0 9 6 8

'^ -3 S 2Β4937Π

Let valve 158 provided, both on heat and on Pressure responds and constantly lets the mixed amount out through a platinum grid that allows nothing but that in the open air forms steam.

Leave the explosion limits or the limits of flammability define themselves by the limiting composition of a combustible gas and oxygen or air mixture, below which the mixture does not ignite or does not continue to burn. In other words: a gas-oxygen mixture outside of this Limits cannot generate heat to a sufficient extent to cause combustion to occur under the conditions of the Try self-propelling / The lower limit of flammability represents the smallest proportion of gas that * when mixed with oxygen or air burns without constant heat must be supplied from an external source. Above the upper limit, the large proportion of what is present acts combustible gas as a diluent so that the combustion cannot, in turn, advance itself.

In the ordinary combustion of a gas, the temperature lies not the whole gas-oxygen mixture at the ignition point. Combustion begins with externally supplied heat at a single point and the heat generated by this combustion serves to bring the rest of the mixture to the ignition temperaturea. In order for this to take place it is necessary that the circumstances of gas and oxygen in the mixture are within the limits of flammability, otherwise no combustion takes place, finds.

6U98 19/0968

-W- 36

The ranges of flammability limits of hydrogen in oxygen and air at atmospheric temperature and pressure are:

:: Limits as percent by volume: Limits as percent:: in oxygen: by volume in air

: Gas: Percent: Percent: Percent: Percent:: lower limit: upper limit: lower limit:> upper limit- :: Mixture: Mixture: Mixture: Mixture

4.65

95.9

6.2

71.4

Pressure increased above atmospheric pressure lowers the upper and lower limits of the flammability of hydrogen. Therefore, at high pressure, more hydrogen is required to form a lower limit mixture, and more oxygen or air is required to form an upper limit mixture. Above, the working temperature given for this example is given as 427 C (700 ^c K). This working temperature is 153 ° centigrade (307 ° F) below the ignition temperature of hydrogen in oxygen or air.

The unit can be operated in two different ways: In the first manner, shown in FIGS. 9 and 10, the unit also supplies pure hydrogen as a product via line 142

6 U 9 8 1 9/0968

77--

3? 3βθ

an interference of less than 1 % oxygen. This hydrogen is safe at any temperature because it is non-flammable without at least 6.1% oxygen or 28.6 % air.

In the second operating mode shown in Pig. 11, the Unit a mixture or a mixed mixture of hydrogen and oxygen. In the alternative, schematically in Pig. 11 In the embodiment shown, a reaction chamber 16O generates 710 g of hydrogen from 6,343 g of steam, which is via the steam line 26 access. The hydrogen exits a line 162 and reaches a section A of a partial valve 164, where 387 g Hydrogen through line 166 into reaction chamber I68 be branched off where the reactant is regenerated. The remainder of the hydrogen goes from the partial valve 164 to a line I70. In the meantime, the 387 g of hydrogen set 3,073 g of oxygen in the reaction chamber I68 free and an additional 2,560 g of oxygen are released through disproportionation. The hydrogen-oxygen -Mixture leaves the reaction chamber 168 via a line 17 2 of a section B of the partial valve 164. 3.284 g of the hydrogen-oxygen mixture pass through a line 174 back to the steam collector 20, where they are converted back to water by means of the catalytic converter 140. The remaining 2,736 g the hydrogen-oxygen mixture go through a line 176 and the safety valve I58 to a division T 178 where they mix with the hydrogen in line 170 to then to be withdrawn to be used for a job.

1-609819 / 0968 - ^c fg - *

atf

Although the steam collector operates at approximately 155 x 453.59 g pressure, atmospheric pressure is maintained for the gases hydrogen and oxygen. It is possible to use the gases if they are the Reaction chambers leave to catalyze, so that instead of hydrogen and oxygen, water flows through the pipes when there is

it is desirable to process the gases at 155 psi (psi = 453.59 g / 6.452 cm) in order to make the vapor pressures compatible with the gas pressures to do and vice versa.

In the calculations to determine the amount required for preheating Heat, an amount of 21.097 g of the manganese reactant was assumed. This is based on an exemplary design, in which the outer cylinder 88 has an inner diameter of 15.24 cm and a working length of 81.28 cm and the inner cylinder has an outside diameter of 11.43 cm, an inside diameter of 10.16 cm, and a working length of 81.28 cm. Using the

Equation for the volume of the cylinder, T "r l, where R is the radius and L is the length, the volume of the interior of the exterior

-z

The outer cylinder is 905 x 16.387 cm, the outside of the inner cylinder 90 is 509 x 16.387 cm, and the inside of the inner cylinder 90 is 402 χ 16.387 cm. If the outer volume of the inner cylinder 90 is subtracted from the total inner volume of the outer cylinder 88, then the volume of the annular reaction chamber 116 is 396 × 16.387 cm. The volumes of the outer reaction chamber II6 and the inner reaction chamber are therefore approximately the same (396 16.387 cm- ⁵ and 402 χ 16.387 cm ^). The random manganese schnitzel has a ^T density of about 248 x 453.59 g per 0.02832 nP.

6098 19/0968

f · V ■ "" ·

For a better understanding of the partial valve 1 ^ 0, reference is made to FIGS. 12 to 15. The partial valve 130 comprises a body 178, a wire member 180, an outlet member 182, an upper end plate 184 and a lower end plate 186. As shown in Fig. 1 ^ the partial valve 1 ^ 0 is formed by two valves held together, with upper and lower sections being provided . In order to facilitate the description of the valve, only one of these sections will be described in detail, the other section being identical. A gas inlet opening 188 merges into an inlet end 190 of a passage 192 in the rotating part I80. The gas then exits an outlet 194 of the passage 192 and flows according to Figure 12 through a passage to an outlet opening I96 I98 in the outlet member 182. When the Drshteil is fully rotated into its second position, the outlet end 19 drops ² J- the passage I92 with a passage 200 together and the gas leaves the sub-valve through an outlet opening 202 in outlet member 182. The sub-valve is continuously adjustable so that at any intermediate position between the extremes just discussed, the gas flow is divided and in proportional proportions through passages I96 and 200 as well the outlet ports 198 and 202 flows.

14 and 15, the rotating part I80 has a body 204 and a shaft 206. The body 204 has a pair of identical passages 192. The inlet end 190 of the Passage 192 is larger than outlet end 194 so that the Gas flow in the passage I92 of the rotating part I80 is not interrupted when the rotating part is moved from one position to another.

609819/0 9 68 - ■ / €€ -

The structure and mode of operation of the control valve 1O6 result well from Pig. 16 to 19 · According to Fig.i6, the control valve has a Body member 2θ8, an elongated valve element 210, which is in a

Cylinder 212 is reciprocable, an upper cover plate 214 and a lower cover plate 216 and a side plate 218. The control valve 1θ6 can be made of any suitable material, however, in terms of the overall device prevailing temperature conditions stainless steel JO ^ preferred is.

The body member 2o8 comprises a machined or cast elongated cylinder 212 having a diameter suitable for to accommodate the valve element with minimal play - the limb 208 also has a plurality of inlet ports 220 and front and rear outlet ports 222,224. The names "anterior" and "posterior" are used for convenience only and are not intended to have anything to do with location or arrangement of the control valve 206 say. The control valve 1θ6 is shown in a vertical position, but can also be in a horizontal position or arrange in any other position. Inlet port 220 and outlet ports 222 and 224 are through the Body member 208 bored and are so with the cylinder 212 in connection. An inner inlet port 226 communicates with the inlet port 220 communicates via duct means 228 at one end and to the rear of cylinder 212 via a Channel facility 2 ^ 0 in connection at the other end. The two Cover panels 214, 216 and side panel 218 are attached to body member 208 by suitable fasteners such as BoI-

6098 19/096 8

? B 4 9 3 7 η

zen, attached.

The valve element 210 is an elongated cylindrical member having a plurality of peripheral slot portions 2J> k and 2j6 which are offset from one another on opposite sides and are longitudinally spaced so that they correspond to the plurality of inlet and outlet ports. The valve element 210 is arranged to be movable to and fro in the cylinder 212 and, as shown in the drawing, is normally resiliently urged upwards, for which purpose a suitable spring device 238, for example a spring, is used. The to-and-fro movement is effected with a conventional external control means 24θ, for example with a solenoid, as is indicated schematically in FIG.

The complete mode of operation of the control valve is clear from FIGS. 16 to 19 but also from FIGS. 9 and 10. Below one of the sections A to D of the control valve according to FIGS. 9 and 10 is described. According to Fig.17 this is Valve member 210 in the normally preferred position so that the slot member 236 is in a position in which it cooperates with the inlet port 220 and the outlet port 222. According to FIG. 18, a fluid which enters the valve through the inlet opening 220 flows into the slot part 236 and then to the outlet port 222. This corresponds to that in Fig.9 position of the control valve shown.

When the valve element 210 is in its second position

609819/0968

1OI - + * - 2 549 3 7Π

found, i.e. in the depressed position according to Pig.i6 and 19, then the slot part 2 ^ 4 with the channel device 2J5O and the outlet port 224 in line. Fluid that passes through the inlet port 220 enters, can not get to the outlet port 222 because of the valve element 210, instead the fluid passed through the channel means 228, the inlet channel 226 and the channel means 2j30 to part through the slot 2 ^ 4 and then out through outlet port 224. That is the position of the control valve shown in Fig.10.

According to the preceding description, the invention is based lying tasks successfully solved. The invention is not limited to the preferred embodiments shown and described limited, but can also be embodied differently and put into practice.

609819/0968

Claims (25)

Claims 1. A method for generating hydrogen by displacement from water by means of a reactant with subsequent regeneration of the reactant, characterized in that a) a reactant is provided which comprises a metal or a metal oxide and is capable of converting hydrogen from water to separate exothermically in order to form an oxide of this metal with a higher oxidation state, which leads to spontaneous dissociation or is capable of disproportionation in the absence of free hydrogen, b) the reactant is heated to a temperature at which it separates hydrogen from water, c) steam is continuously passed over the reactant, the metal oxide having a higher oxidation state and hydrogen are formed exothermically, d) the hydrogen is continuously removed, e) the reactant is monitored to determine when the proportion of the reactant that is in the metal oxide has converted to a higher oxidation level, has reached a predetermined percentage, f) the temperature of the reactant is increased to the temperature at which the metal oxide of higher oxidation state dissociates or disproportionates, the metal or the metal oxide and oxygen are formed, g) the oxygen is continuously removed, h) the reactant is monitored to determine when the -2-609819 / 0968 2 5 49 3 Metal oxide of a higher oxidation level has completely converted back into the metal "or the metal oxide, and i) the steps according to c) "to e) are repeated. 2. The method according to claim 1, characterized in that the reactant is selected from the group consisting of metallic iron, manganese, alloys of iron and manganese and low-level oxides of these metals. 3. The method according to claim 2, characterized in that the reactant is a mesh structure or a continuous thread or continuous band of the metal and is heated according to step b) by passing an electric current through it. 4. The method according to claim 2 or 3, characterized in that steps e) and h) are carried out by measuring the electrical resistance of the reactant to electrical current and comparing it with the known resistance of the metal, metal oxide or a com bination of metal and metal oxide. 5. The method according to claim 2, characterized in that the reactant is in the form of particles and is heated according to step b) by means of a heating element embedded in the particles. ■ '■ 609819/0968 254937Γ) 6. The method according to any one of the preceding claims, characterized in that the generation of hydrogen is continuously reactive and that a) a plurality of reaction chambers is provided, each of which receives a reactant which is a metal or an oxide thereof and capable of exothermic separating hydrogen from water to form an oxide of this metal with higher oxidation state, leading to dissociation or disproportionation in the absence of free hydrogen is spontaneously capable b) the reactant is heated in a first half of the reaction chambers to a temperature at which it is hydrogen separates from water, c) steam is continuously passed over the heated reactant, the metal oxide of a higher oxidation state and hydrogen being formed exothermically, e) steps b) to d) are carried out in the second half of the plurality of reaction chambers, f) the temperature of the reactant in the first half the reaction chambers is increased to the temperature at which the metal oxide of higher oxidation state dissociates or disproportionated, whereby the metal or the oxide of the metal and oxygen are formed, g) the hydrogen is continuously moved away, h) steps c) to d) are repeated in the first half of the plurality of reaction chambers, -4- 609819/0968 406 254937Π 1) steps f) and g) in the second half of the plurality be carried out by reaction chambers, and 2) steps c) to d) and f) and g) are repeated intermittently in each half of the plurality of reaction chambers for hydrogen generation and reactant regeneration, the hydrogen generation phase in one half of the plurality of reaction chambers concurrently with the reactant regeneration phase in the other half the plurality of reaction chambers takes place. 7. The method according to claim 6, characterized in that two reaction chambers are provided. 8. The method according to claim 6, characterized in that six reaction chambers are provided. 9. The method according spoke 6, characterized in that the hydrogen generation and reactant regeneration phases are carried out alternately in a predetermined time cycle in the first half of the reaction chambers with the second half of the reaction chambers. 10. The method according to claim 9, characterized in that the predetermined time cycle lasts from one to three minutes. 609819/0968 / 3- 254937Π 11. The method according to claim 10, characterized in that the predetermined time cycle lasts two minutes. 12. The method according to claim 6, characterized in that the composition of the reactant in the first half and in the second half of the reaction chamber is monitored with regard to the percentage of metal and oxide of the metal and of metal oxide of higher oxidation level and the alternating in the first Half and the second half of the reaction chambers taking place hydrogen generation and reactant regeneration phases is carried out according to the composition of the reactant in the first half and the second half of the reaction chambers. 13. The method according to any one of the preceding claims, characterized in that a metal oxide which is capable of dissociation or disproportionation in the absence of free oxygen is reduced for the purpose of forming the corresponding metal by the metal oxide in the absence of free oxygen to the temperature at which dissociates or disproportionates the metal oxide, is heated and the oxygen formed is continuously moved away. 14. The method according to claim 13, characterized in that the metal is iron, manganese or an alloy of iron and manganese. -6- 60981 9/0968 ^1O * 2 5 4 9 3 7 Π 15. Device for generating hydrogen by displacement from water by means of a reactant with subsequent regeneration of the reactant, characterized in that it has a) a plurality of reaction chambers (14), b) in each reaction chamber a reactant (18) which comprises a metal or metal oxide and is capable of exothermic separating hydrogen from water to form an oxide of this To form metal with a higher oxidation state, which leads to spontaneous dissociation or disproportionation in Absence of free oxygen is able to c) means for heating the reactant to a temperature at which it separates hydrogen from water, d) devices (20, 48) for generating steam Water, e) conduit means (26) to conduct steam from the means for generating to the reaction chambers, f) Means (30, 34) to remove hydrogen from the reaction chambers to derive g) valve means (40) to remove steam from the line means optionally a first part of the reaction chambers or a second part of the reaction chambers feed to in the reaction chambers that are currently Steam is supplied to produce hydrogen and h) control devices to operate the heating devices as required and around the valve devices to operate so that steam to either the first portion or the second portion of the -7- 6098 19/0968 254937Π Reaction chambers for the purpose of generating hydrogen is passed and the same time the flow of steam to the second portion or the first portion of the reaction chambers is interrupted for the purpose of regenerating the reactant. 16. Gate device according to claim 15, characterized in that the plurality of reaction chambers comprises six tubular chambers (14) and an additional tubular, a heating device (16) receiving chamber is provided, which serves as a steam preheating chamber, devices are provided which directing a stream of steam into this steam preheating chamber and then in turn into each of three of the six chambers, six of the chambers being arranged in a circular order and the seventh chamber being arranged in the middle of this circular order. 17. The device according to claim 15, characterized in that the valve devices also direct a reaction-inert gas into the half of the chambers intended for the regeneration of the reactant. 18. The device according to claim 15, characterized in that the reactant (18) is iron or manganese or a combination thereof and has the following form: wire, tape, gauze, lumps, chips, pellets or powder. -8th- 609 8 19/0968 19. The device according to claim 15, characterized in that the plurality of reaction chambers comprises two chambers which are delimited by a pair of tubular cylinders (88, 90) of different diameters and concentric to one another, the space in the inner cylinder being one of the chambers (114, 116) and the annular space between the two cylinders forms the other chamber and the volumes of the two chambers due to corresponding The cylinder diameters are approximately equal to each other. 20. Apparatus according to claim 18, characterized in that the reactant (18) is in the form of particles and the heating device is an electrical heating element embedded in the reactant. 21. The device according to claim 18, characterized in that the valve devices (106) conduct a portion of the hydrogen generated in the reaction chambers in the hydrogen generation phase into the other reaction chambers in the reactant regeneration phase to reduce that generated in the other reaction chambers Purifying oxygen, directing the remainder of the hydrogen to and through the hydrogen-carrying devices and the hydrogen-oxygen mixture generated in the other reaction chambers out of these other reaction chambers. 609819/0968 7549370 22. The device according to claim 21, characterized in that additional valve devices (130) are provided to guide the hydrogen out of the hydrogen-carrying devices and the hydrogen-oxygen mixture out of the device when they are in a first position, and to to the devices (20, 48) for generating steam when they are in a second position, the hydrogen and oxygen being catalytically converted back into water and the additional valve devices continuously variably adjustable between the first position and the second position are. 23. Device according to one of claims 15 to 22, characterized in that a fluid control valve (106) for simultaneous control of a variety of Plude provided is which includes a) a limb (208) having a front and back, one extending longitudinally therethrough Bore and a plurality of longitudinally spaced valve sections, wherein each section has a bore in communication on the front of the limb Inlet opening, at the front of the limb a first outlet opening communicating with the bore, at the rear of the limb an outlet opening communicating with the bore and inner one Channel means, which the inlet opening with the 6098 19/0968 Connect the bore at its rear end, and b) a valve element reciprocable in the bore (210), which has a plurality of longitudinally spaced apart first slot parts, corresponding in number and spacing of the plurality of sections, and on the opposite side of the valve element a plurality of longitudinally spaced apart second slot parts, which are arranged offset with respect to the first slot parts, wherein when the valve element is in a first position, the first slot parts the inlet opening with the first outlet opening, and then, when the valve element is in a second position, the second slot parts are the internal channel means connect to the second outlet port. 24. The device according to claim 23 » characterized in that the valve element (210) is normally pressed into the first or the second position by means of an alignment device (238). 25. Device according to one of claims 15 to 24, characterized in that a fluid partial valve (130) is provided which has a) a body portion (178) having a longitudinal bore and at least two sections, each of which one with the bore in communication inlet opening and first and second, in the transverse direction at a distance from- -11- 60 9 8 19/0968 having mutually arranged outlet openings opposite the inlet opening with the bore by means of a first and a second channel device are in connection, which are of the same Durchpeeser and to each other the end connected to the bore touch the essential, and b) a cylindrical valve element (180) rotatable in the bore and having one transversely through it for each of the sections Having fluid passage which at one end has a corresponding to the diameters of the channel means Diameter and at the other end one compared to the diameter of the inlet opening about twice as large Having diameter, the valve element is arranged in the bore such that the other end of the passage with the inlet opening and one end of the passage with one or both channel means in communication stands. 609819/0 96